Archdevil

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As the Demon Princes are to Tanar'ri and other demons, so too are Archdevils to Baatezu and other devils. These are the demigod-like rulers of the Nine Hells of Baator, or just plain Hell if you're coming from Pathfinder, the commanders of the diabolic legions and the other major contestants for Big Bad Evil Guys for players to defeat.

Because D&D's devils have a certain Abrahamic influence, there are traditionally far fewer of them than there are Demon Princes; in fact, in some sourcebooks, the Archdevils are the same thing as the Archdukes, which means that if you don't count their boss Asmodeus as one of them, there's only ever eight Arch-Devils in total, plus a handful of former Archdukes who have the power but no longer have the authority. Who's who depends on which edition you're looking at. Other editions make it clear that there Archdevils consist of both Archdukes - the layer rulers - and Dukes, which are Archdevils not quite strong enough to have their own layer.

Pathfinder, in comparison, has a much fuller roster of Archdevils; as well as Infernal Dukes like in D&D, there are also the Malebranche - unique and powerful devils strong enough to ravage worlds themselves, essentially a next tier down from the Infernal Dukes, and the Whore Queens - a band of four female fallen angel archdevils who have risen as high as they can in the misogynistic hierarchy of Hell, and whose cults are comparable to those of the Archdukes.

The Archdukes of Baator

Bel

The Lord of the First in 5e (in prior editions this role was held by Tiamat), Bel is the Hells' premier success story, though in truth he's effectively gotten himself promoted into a corner (no, not a corner office). He frequently uses treachery, double-crossing and ambushes to further his agenda. Bel started out as a powerful Pit Fiend general in service to the Dark Eight, the devil generals in charge of the Blood War. His campaigns against the demons resulted in success after success until he seemingly changed sides and joined the Tanar'ri. When he gained their trust he led them into a battle against the devils, only to betray his demon allies and have them all killed by his forces. He returned to Baator as a hero and became the right-hand devil of Zariel, a fallen angel and then-archduke of Avernus. He served her many centuries and eventually became her lover. This became her undoing as Bel turned her court against the fallen angel and overthrew her. He somehow managed to capture her and slowly strip her of her powers while he declared himself the new Lord of Avernus. Of course, given the fact that they are both devils and he has a long history of working as a deep-cover agent, it could just be an elaborate sex thing. Devils are big on S&M.

He prepared himself from an invasion from the other Archdukes in an attempt to overthrow him and claim Avernus for themselves, but instead he was visited by Martinet, the constable of Asmodeus. He informed Bel that Asmodeus congratulated him on his guile and skill, and was willing to accept him as the new Lord of the First, on the condition that Bel retained his position as a general to the Dark Eight. Somewhat relieved at these terms, Bel accepted. But as is common to those who make deals with devils, he discovered something a little too late: his new duties as the main overseer of the hellish "homefront" of the Blood War meant that he had less time to spend politicking with the rest of the Lords, effectively cutting himself off from further advancement in their hierarchy. The other Archdukes of Hell did not really mind this: they all saw the Pit Fiend as a double-crossing upstart and none of them were willing to accept him as an ally. The only one who sees Bel as more than a nuisance is Asmodeus himself, but even then the Overlord of Hell doesn't really think very highly of him. Funny how for all his previous scheming and undeniable martial prowess (tested daily by the claws, fangs, blades, and spells wielded by the endless hordes of Demonic invaders), Bel was left with the unenviable position of being the Nine Hells' biggest guard dog--in other words, he is in charge of the necessary, even vital, task of keeping the invading Demons out of the lower layers of the Nine Hells, but by earning this "reward" he has exhausted any intraplanar avenues for advancement in Hellish politics. If you're confused about all this, Bel's situation is similar to how a real life guard dog is useful for guarding a company's building, but guard dogs obviously can't become CEO of any organization they're guarding.

As a realist who is somewhat resigned to his lot and who knows he needs all the help he can get just to keep the demons at bay, day after day (what with the Archdukes of the other layers and even the Lawful Evil deities residing on his layer, such as Tiamat and Kurtulmak, being less-than-enthusiastic about aiding him) he is the sole Archduke of Hell who is the most willing to give anyone who can offer credible assistance to his cause a fair hearing. If adventurers approach him with offers regarding taking the fight to the Tanar'ri he is more than willing to listen. Mortals who treat him with respect and without duplicity will find a surprisingly reliable ally, unmatched in the Nine Hells. But if they try to deceive him or fail in their promises, he will display all the rage and cruelty one would expect from an Archduke. He may never be short of demonic punching bags to take out his devilish anger and frustration out on, but he is a devil through and through, and is still one of the nine most powerful devils in all Hell, regardless of his dead-end job.

...But in 5e he and Zariel swapped positions again due to him temporarily loosing his entire FUCKING LAYER to demons, so maybe there's some hope for him now.

Dispater

The Iron Duke is a paranoid individual. He has good reason for this, being sandwiched between a power-hungry social climber and the greediest motherfucker in existence, but even considering that his paranoia defies reason. He mainly sits in the Iron Tower, his citadel. In here he is completely invulnerable, which is why he seldom leaves it, not even to meet with his peers or Asmodeus himself. The Lord of the Second is no coward though: he is calm, composed and well-mannered, even when angered. He is the infernal patron of strife and discord, and this is mirrored in his obsession with spy-games and intrigue. He acts though intermediaries to engage in his plots, where he employs some of the most loyal devils in the Hells to fit his mad control-freak nature: aside from large numbers of Erinyes he also has scores of iron golems and other such trustworthy, unbribable, mindless constructs that follow his every command. Dispater is very skilled at the political games of Baator, where he is conservative, careful and methodical. He is usually allied with Mephistopheles because the two of them have worked together all the way back when they first came to Baator, and they ally against the hated Baalzebul who in Dispater's eyes deserves no respect since he is a fallen archon rather than a "true" devil.

Mammon

Mammon is a selfish being, even for a devil. He is a patron of material greed and is frequent in his betrayals. His treacherous nature has made him very unpopular with the other Lords, meaning none will even consider striking an alliance with him. With no opportunities for alliances left in the Nine Hells, he has instead he turned to the Prime Material Plane to gain power, corrupting rich and powerful mortals to become greedy and lecherous monsters and eventually signing their souls over to him, essentially banking on the old saying "the love of money is the root of all evil." As a result of having no friends, the Lord of the Third is a very paranoid devil and will punish his servants at the slightest provocation by demoting them. This high turnover rate means that Mammon also promotes more devils more frequently than any other Lord, and will pay a good price for a soul fitting for a specific promotion. Noticing the cycle here?

He once had an affair with Glasya, but after his role in the Reckoning Asmodeus forced his daughter to end the relationship, and left Mammon with a new form consisting of a male humanoid upper torso and a snake-like lower body as a mark of shame. Both Mammon and Glasya seem to bow to Asmodeus' command, but some claim that now that she's no longer right under her father's nose Glasya has rekindled the relationship. Others claim that she despises Mammon for not fighting for their relationship. It's even possible that both are true, though how they manage an affair around Old Scratch turning Mammon into a snake-man to give him the "Walter Peck" treatment is a riddle for the ages. Whatever the case, since Glasya's ascension Mammon has redoubled his effort to increase the flow of souls to his realm by corrupting the Material World via appealing to its inhabitants' greed, and increasing his power when they sign over their souls to him or his minions. Unlike Baalzebul's punishment, Mammon can re-adopt his original form of a bloated Pit Fiend when he wants, but only for 10 minutes per Hit Dice a day, whereupon he must endure the frustration of turning back into his new form, which he takes out on his servants and his endless quest for more riches and souls.

It's worth noting that he lives in a city perpetually sinking into a swamp, so one can't help but wonder if this might be connected to the fact he sits on a pile of more gold than even a dragon would ever think they needed.

Belial and Fierna

The twin Lords of Phlegethos, Belial and Fierna are a father and daughter pair who run the Fourth layer jointly. After a failed coup that Belial was a part of, he offered to share power with his daughter Fierna to appease Asmodeus. He accepted and so Fierna became the co-ruler of Phlegethos. Both of them look almost completely human, aside from their horns and clawed fingers. Both are rather attractive with sadistic personalities: they revel in killing and bloodshed. But they are no fools and will retreat when in trouble. Belial is very much a traditional devil: he's cautious, scheming and making plans to overthrow his fellow devils. He personally trains his daughter in how to be a good devil, including personally taking a hand in teaching her about "love and pain", which is exactly what it sounds like. Bleh.

Fierna is more of a free spirit, enjoying the life of a spoiled daughter-turned-figurehead leader of Phlegethos. But things began to change when Glasya came to the scene. This thwarted Belial's plot to invade Malbolge because attacking the freshly-established Lord of the Sixth is a Very Bad Idea when you're still going to be working for her dad after you're done. His plots were further compromised when Fierna and Glasya really hit it off at a hell party. The two quickly became best friends, bonding over the rigors of having an Infernal Duke for a parent, much to Belial's chagrin. He sees Glasya as a bad influence who puts all sorts of naughty ideas into his daughter's head. This would be kind of sweet, if said ideas did not include the gruesome murder of many of his more-loyal subordinates. And for the fact that Glasya murdered Naome, Belial's consort and Fierna's mother in her plot to start the Reckoning. Fierna is rapidly becoming the biggest threat to her father's reign, and it seems only a matter of time before the one-time hellish party girl will attempt a coup of her own. Of course, given infernal ethics, Belial will probably be rather proud when she finally kills him... probably.

She's also started dating a pit fiend, Gazra the commander of the Hamatulas, who doesn't like her dad much either. Levistus is making a bid for his loyalty, but the smart money's on him turning the old fart down.

Levistus

The Lord of Stygia is currently in quite a predicament. The handsome and mostly-human-looking (his completely black eyes are something of a giveaway) rogue archduke is trapped in an indestructible prison, locked away by Asmodeus for the crime of murdering Bensozia, the Overlord's queen and Glasya's mother. It is told Levistus attempted to seduce her away from her husband, in both senses of the word, and when Bensozia told him to get bent, he killed her in a fit of rage. Asmodeus's punishment was swift: Levistus was imprisoned in a massive glacier more than half a mile across, completely impervious to any sort of magical or mundane damage. This prison floats in the waters of Stygia, occasionally drifting into and out of the Styx.

The truth however is more perplexing. Asmodeus' consort, Bensozia, never loved the big man. But since he is the Overlord of Hell she couldn't exacty just dump him because that would make him look bad, which would have dire consequences for her. So she approached Levistus whom she started to push towards a coup, and the two began to have an affair. Levistus however had trouble keeping it in his pants and seduced Glasya, with whom he also started an affair. When the Princess of Hell had a big fight with daddy she stormed off to Levistus and wanted to become his consort. Instead she found him balls-deep in her mom. In a fit of rage and jealousy she murdered Bensozia. If this were to come out Asmodeus' position would be rather damaged, so the big man's majordomo had the idea to pin the blame on Levistus instead. And so Levistus ended up as a popsicle. This would have been the end of Levistus, were it not for one of the most perplexing turn of events in Hell.

After the rebellion of several Archdukes, Asmodeus made the bewildering decision to strip Geryon, the only archduke that remained loyal to him during these events, of his title of Archduke and force him into exile. In his place, he appointed Levistus as the new Lord of the Fifth. But Asmodeus cleverly avoided either imbuing Levistus with the proper mantle of an Archduke or freeing the murderer from his icy prison. Since that day, Levistus' minions have tried to free their old boss using every possible weapon, magic, trick, and skill check they can scrounge up, even sacrificing good-aligned fire creatures in a bid to destroy the prison, but thus far nothing has worked. The fact that he is still imprisoned fills Levistus with hate: for his fellow Archdukes, who naturally shun him like a leper, for Glasya and her rise, and most especially for Old Scratch himself. As such he is working tirelessly to subvert the courts of the other archdukes by planting spies in their courts, working through avatars and long-range communications for obvious reasons. He plans to make overtures to Glasya in order to see if she would be willing to aid in overthrowing her father. Whether or not he knows that Glasya hates him and would use any possible justification to destroy Levistus that presents itself is unknown. Perhaps he does and will try to avert this, trying to be more careful than the last time he tried to turn someone close to Asmodeus against him.

Glasya

Named after Glasya-Labolas, the demon from the Ars Goetia that provides the name of another big-name villain in a franchise belonging to Wizards of the Coast, Glasya is the daughter of Asmodeus and the current Lord of the Sixth. She looks like a beautiful young woman with brown skin, wings, a tail with a half-moon shaped tip and a pair of horns jutting out of her forehead. She is more than willing to lure unsuspecting victims into her embrace, only for her to release a virulent disease that sloughs the flesh from their bones and has them suffer a hideously painful death, with the last thing they hear being Glasya's laughter. Fortunately for their relationship, Mammon's totally into that.

Glasya overthrew the previous ruler of Malbolge by making her predecessor gruesomely explode and reshaping the layer forever. Any who challenge her rule or, even worse, humiliate her will receive endless sessions of hideous torment. She is very sadistic and enjoys both observing and inflicting torture, training many highly-skilled servants in the infliction of pain. The Princess of Hell urges her cultists to experiment in various ways to increase their depravity, readying them for an as-of-yet unknown goal. She gets along great with Fierna, since they're very alike, and has started turning her against her father, Belial. Glasya might also have rekindled her relationship with Mammon, but both go to great lengths to keep whatever's going on between them to themselves. Officially she despises Levistus and wants to destroy him in revenge of her mother's death, but as of yet is unable to do so, because her father wants her to first maneuver him into breaking infernal law first, as a training exercise. Unofficially she wants to do this to prevent the truth coming out that she murdered her mother, not Levistus. While in his prison Levistus is safe, but Glasya will take the first opportunity she gets to destroy him. The others lords keep their distance, mainly because they see her as a tool of Asmodeus to consolidate his rule over the Hells. Outwardly she seems loyal to her father, but since she is a devil it is only a matter of time before she will turn against him. Old Scratch brought her up "right," after all.

Baalzebul

Baalzebul is one of the middle crop of infernal dukes. Back in the day, Baalzebul was known as the archon Triel. Triel was a very selfish perfectionist who kept wanting more and more out of his existence, which eventually caused his fall from grace. After being welcomed into hell, Triel rose through the ranks and attained the title of the Lord of the Flies, supposedly because his webs of intrigue were so tight that not even a fly could slip past him, though many pointed to the archduke's multifaceted, fly-like eyes.

Baalzebul eventually made his way to the rank of archduke and partook in the rebellion against Asmodeus. He was defeated but, though clever maneuvering, managed to hold onto his lordship anyway. All the same Asmodeus had his revenge and cursed him such that Baalzebul instantly has to spend a year in the slug form on the right every time he lies to another devil... including all the lies he told before that curse was placed, meaning he had to go through a several-thousand-year span of being in this state and only recently was able to return to his true form again. But while in this form, Baalzebul is easily the most grotesque and disgusting of all the archdukes. Presumably it is his own ego that prevents such a clever bastard as him from exploiting the loophole in this curse, a loophole which surely would be obvious to any devil worth their salt: the curse is completely useless as a lie detector if he lies to someone while already in slug form. (Presumably he wanted his true form back more than he wanted to lie to other devils.)

To this day Baalzebul craves the downfall of Asmodeus as revenge for this humiliation. Thus far, he's had little success with this plan, but the Lord of the Flies has established a notable cultist presence on the Material Plane through a combination of lies, charm and promises of power. Aside from Asmodeus, Baalzebul despises Mephistopheles, who was one of his opponents during the rebellion in Hell. He counts Belial as an ally, but Fierna's relationship with Glasya and her growing power base makes this alliance at best unreliable.

Mephistopheles

The Eighth Archduke looks like the classical fictional devil: red, big, horned, winged, clawed, fire-cloaked, still kinda handsome, and so on. As the second most powerful devil of Baator, there is only one way for the Lord of the Eight to go upwards: he has to overthrow Asmodeus himself. Nearly every moment of his existence is spent plotting towards this end. He is a being of pure ambition and avarice, incapable of satisfaction with anything less than supreme power over Hell itself. He is currently the steward of the only known permanent planar portal into Nessus, commanding the armies that protect the gates into the last layer of Baator with his vast armies of Ice Devils and Pit Fiends. Because of this limitless ambition he has alienated himself from all but a few archdukes. One of his few allies is Dispater, with whom he has an alliance that dates all the way back to the days of the founding of Baator.

Mephistopheles' ego is his biggest flaw. He sees himself as the rightful ruler of Hell, superior to all of his peers. He especially hates Baalzebul, seeing him as a pretender and no "true devil," since the latter is a fallen Archon. He also sees the Lord of Lies as a threat to Asmodeus, and thus a threat to his own inevitable lordship over Baator. The Lord of the Eight does not really have a strong cultist presence on the Material Plane. Mortals often confuse him with Asmodeus, which rather infuriates Mephistopheles. Why Asmodeus puts up with Mephistopheles is unknown, but it is possibly because of a devil-you-know scenario, or because his struggle with Baalzebul keeps Asmodeus' position more secure.

In a bid to increase his power, he has also developed a unique Hellish magic, simply called Hellfire, which has the unique ability to bypass any amount of fire resistance or fire immunity as it is not merely magical fire but instead powered by the primal energy of the Nine Hells. By calling himself a "God of Hellfire" and gifting mortal servants, unwitting or otherwise, with access to this magic he is banking on getting a steady supply of souls to his layer, because as a certain other fictional universe knows, there's always war going on somewhere in the multiverse and therefore no lack of combatants wanting for effective weapons and offensive magic. The creation of Hellfire and highly destructive constructs using it known as "Hellfire Engines" has also indirectly bolstered the forces of the Nine Hells in the Blood War, because Hellfire will reduce virtually any Demon to smouldering cinders just as easily it would a Fire Elemental (fancy that). For some reason Mephistopheles has also seen fit to use Hellfire for mundane heating purposes on his home layer of Cania, which just happens to be the coldest layer of the Nine Hells, so cold that the weather outside of the "warm zones" he's created will freeze non-Devils without cold immunity or a special permit from Mephistopheles protecting travelers from Cania's hellishly cold weather (but not cold damage of any other kind) solid within minutes. It's gotten to the point that many of his Ice Devil servants have deserted his warm abode on Cania and are trying to work their way back into his good graces by coming up with an offensive cold spell more to their liking than "distinctly un-Canian fire magic."

Mephistopheles also had a pretty big part in the Hordes of the Underdark campaign in Neverwinter Nights, where he was the BBEG (not really a spoiler), and gets a lot of interesting backstory. He has a pretty cool, semi-original plan to beat Asmodeus that is, naturally, foiled by a PC and his gang of badass heroes.

Asmodeus

The Overlord of Hell, Asmodeus is the uncontested ruler of Baator. All devils eventually answer to him in some way or the other, either directly, indirectly or through subterfuge. He has his own article, which can be found here.

Other Archdukes

Over the eons various archdukes have risen and fallen, overthrowing their masters and being kicked out of office by their underlings. A few of them are notable in the history of Baator.

Zariel, Lord of the First

Zariel

The previous Lord of the First, Zariel was a fallen angel with burned wings and a piercing gaze. She had Bel as her loyal servant, general and perhaps lover too. To her folly she trusted him too much, which eventually lead him to turn her court against her and imprisoning her. Ever since she remained locked up in the dungeons of the Bronze Citadel, where she is drained of her power by Bel and has her flesh cut up and fed to the lord.

In 5e however there was a change of power: by decree of Asmodeus Zariel was freed and reinstated as the Lord of the First while Bel was demoted to her adviser, because Asmodeus preferred her aggressive risk-taking approach over Bels cautious and reserved one, since Bel actually temporarily lost his entire fucking layer to demons at one point. The exact reason behind this is unknown and likely to remain unexplained until the next version of the Fiendish Codex or The Manual of the Planes is released. (Told you the whole deposing plot was a sex thing.)

Geryon, former Lord of the Fifth

Geryon, Former Lord of the Fifth

The devil Geryon ruled the Fifth for many centuries. At least until the Reckoning, where Geryon was the only Archduke to rise in the defense of Asmodeus. The reward for his loyalty was to be deposed and have Levistus reinstated (although never freed from his icy prison).

What happened to Geryon remained a bit of a mystery, though it is said that after the betrayal he began to doubt his actions and lost all hope at which point Asmodeus struck him down even further, obliterating him. Some believe that the energy was never transferred back to Levistus, since why would he need it if buried under a glacier of ice? The story goes that Levistus was being used as a novel distraction for the rest of the Archdukes and that Geryon's energy was being stored until Asmodeus' daughter Glasya was ready to be promoted to rulership over the Sixth layer.

As for Geryon himself, stripped of his power, what remained of his essence departed into that in-between space where Vestiges go, granting those who seek him out powerful vision bonuses and a gaze attack, though his influence is to force his binders into becoming overly trusting to the point of being dangerously naive.

...But then he somehow got better in 5e. Mordenkaine's tome of foes has a section on the Archdevil cults which notes that Geryon's consists of individuals with whom he strikes bargains. Those who seek brute strength like orcs, trolls and ogres are often drawn into the fold. This means that despite being deposed he still has some degree of power.

Malagard, The Hag Countess

A former adviser of Moloch, the previous Lord of the Sixth. The Hag Countess was not a devil or even a fallen angel. Malagard was a Night Hag, an evil creature normally living on the Gray Wastes of Hades. She was a prominent member of Moloch's court and possibly also his lover (try getting that horrifying image out of your head). During the Reckoning she encouraged her lord to rise up against Asmodeus, which he did fervently. Malagard meanwhile was in correspondence with the loyal Geryon, plotting his downfall. When the gig was up Moloch was the only lord who defied Asmodeus because Malagard told him that Asmodeus would respect his strength if he did. Asmodeus was of course not amused and stripped Moloch of his power, replacing him with Malagard. The new Lord of the Sixth quickly booted Moloch out, and the former lord is on the run since. She used to visit her nobles in disguise, so those who treated mysterious visitors with disrespect quickly found themselves at the ire of their lord. Malagard knew better than to test her political mettle with the other lords and instead aimed for something higher: godhood. She knew all the other lords were just pretenders and no true powers and as such was not content with just being one of them. Malagard frequently went to the Astral Plane to study the dead gods floating around there, but she made little progress in her research as to what the essence of godhood is.

The Hag Countess met an extremely gruesome end. One day she began to suffer terrible spasms and began to swell to beyond grotesque proportions. With her the entire layer changed, from a vast slope into a more level surface. Her body was torn apart; her fingers turned into spires, her hair into a grotesque forest, her ribs became bizarre mountain ranges and her skull grew to the size of a citadel, which is used by Glasya to this day. This proved to be the permanent undoing of the Hag Countess, replaced by Asmodeus’ daughter. This is likely the reason that the Overlord of Hell chose such an unusual being as the Lord of the Sixth: she was meant as a placeholder until he could tame Glasya and have her take responsibility. With the demise of Malagard it seemed that this time was ripe, making the former lord useless.

Moloch, former Lord of the Sixth

Moloch, Former Lord of the Sixth

Moloch was once the lord of the Sixth. During his time the Reckoning of Hell took place, which saw him on the side of Baalzebul alongside his fellow fallen Celestials. After being humiliated and defeated he and his fellow Archdukes were summoned to appear before Asmodeus to grovel. Moloch, being a dumbass, took the advice of his adviser/consort Malagard to defy Asmodeus. Instead of begging like his peers he proverbally whipped out his dick and invited Asmodeus to suck it. Looking at this display unimpressed for an uncomfortable long amount of time he kicked Moloch out and stripped him of his powers as an Archduke before he hit the ground. Malagard, not expecting this to actually work, laughed her ass off all the while and kicked the loser out before being imbued with the power of the Lord of the Sixth.

Now a refugee, Moloch started to plot revenge. Alternating between Baator and the Material Plane, he gathered whatever forces and power he can in an attempt to get revenge. One of his plots involved the Apocalypse Stone, a very high-level module for AD&D involving the end of the world. Moloch is currently still at large.

Gargauth, "Lord of the Tenth"

Gargauth
Broken animal horn
Alignment Lawful Evil
Divine Rank Demigod / Arch-Devil
Pantheon Faerûn
Portfolio Betrayal, Cruelty, Corruption, Power
Domains Charm, Evil, Law, Trickery
Home Plane Prime Material Plane
Worshippers Corrupt politicians, Sorcerers, Traitors
Favoured Weapon Corruptor (Dagger)

Worshipped by some in Faerun as a demigod of corruption and betrayal. He was apparently exiled from Baator because he was too much of a handful for the other Archdukes of Hell, though much of what happened is never actually revealed. He was probably just a casualty of the politics of hell, but rather than being cast down or destroyed, he managed to get out.

Afterwards He travelled the planes, returning to Toril time and time again. He spreads his cults and corruption around, with the aim of ensnaring the planet and dragging it back to the Nine Hells where he can rule it as a Tenth layer, because it worked so well for Mephistopheles when he tried it. Though he is also opposed to other evil deities like Shar and Cyric.

The fact that Gargauth holds some actual divine status shows that he could have been a serious power player in the politics of Hell, since it took Asmodeus so long to attain similar status for himself. Although that also illustrates the point that personal power alone can mean very little on the planes when the Archdukes of the Nine had much more widespread influence and control.

Infernal Dukes

In contrast to the above, these Archdevils never were rulers of the nine layers of Baator, but they're still powerful figures in their own right.

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Bael

A powerful vassal of Mammon, who is also known as the Bronze General. Whilst he's a brilliant tactician, politically, he's kind of inept.

Hutijin

An ascended pit fiend servant of Mephistopheles renowned for both his loyalty to his master and his hatred for mortals.

Titivilus

A scheming archdevil imp who serves as seneschal to Dispater, and may be usurping power right from under his paranoid master's nose.

The Archdukes of Hell

In Pathfinder, these are the reigning archdevils of Hell.

Barbatos

Named after a minor fiendish noble mentioned a few times throughout the books, Barbatos is the gatekeeper of hell. He's not a devil or even a fiend: he resembles some kind of hunched being made from barbed tentacle vines. He protects Hell from invasions by angels and demons alike and makes sure that the souls of the damned are ferried to their final fates. Him not being a devil harkens back to the Hag Countess Malagard, who just like Barbatos is from outside of the plane. Except she's a Hag and Barbatos is... well, it's not entirely clear.

Dispater

Dispater and Asmodeus go way back even in Pathfinder. This grants him a favored place in Hell, but he generally keeps out of infernal politics. Instead he focusses on building the perfect society in which everyone, not just the devils, can live. Given that this community is literally made in Hell, this is not a good thing. In a sense he's an ideal king: calm, deliberate and careful, but he's also ruthless, manipulative and unforgiving. Dispater is big on etiquette as well, and violating it is a surefire way to draw his ire. Yet strangely he also values courtly love and marriage, making him unique amongst his fellow Archdevils. Dispater looks like a typical devil: a horned, red-skinned humanoid with flames crowning his head and tipping his tail.

Mammon

The punchline to all "evil bankers" jokes, Mammon is the treasurer of Hell. A fallen angel, Mammon was slain long ago. But instead of passing on his soul jealously clinged to existence and managed to infuse himself into the wealth that surrounded his place of death. Mammon eventually managed to bind himself to these riches, making him one with the treasures of Hell. He meticulously keeps track of Hell's finances and reports them directly to Asmodeus. Mammon can easily possess objects or people of any kind, but his favorite body is a construct called the Argent Prince that looks like an idealized form of his old body, and grants Mammon a buttload of immunities and abilities.

Belial

The Pale Kiss is a creation of Asmodeus himself. Only the Prince of Darkness himself knows exactly what Belial is or where he came from, and Belial does not seem to care. He can take just about any form he wants almost subconsciously, taking whatever form is most desirable for whoever looks at him. This is one of the purposes for which Belial was created: Asmodeus also granted him boundless imagination and creativity in order to create objects of incredible beauty and cruelty. Belial has created everything from art to weapons, magics and even races of servitors, but once he's done with something Belial gets bored and moves on. On top of his creativity Belial is also a creature of boundless lust, and there are innumerable half-fiends out there of every kind who can trace their lineage back to the Pale Kiss.

Geryon

Greatly resembling his D&D counterpart, Geryon is the lord of Stygia. He did not start out as a devil: he was once an Asura rana, one of the greatest accidents of the gods. When Asmodeus came rolling into town he made a deal with the Prince of Darkness, betrayed his fellow Asuras and strengthened the devils' grip on the plane. In return for his services Geryon was made into an Archdevil. He has unrivaled knowledge of impossible religious truth and the gravest heresies, being more or less the librarian of Hell. Geryon looks a lot like his D&D counterpart: a massive devilish humanoid with the lower body of a snake. Except he's three snakes; one red, one yellow and one blue. The yellow one wields a flail, the blue one carries a shield and the red one carries a great horn that twists the perception of whoever hears it. According to Bestiary 6, he's literally the three snakes; each one can simply regurgitate part of any being it's ever eaten and use it to interact.

Moloch

As the general of Hell, it is Moloch's job to lead its armies to victory all across the planes. He does not only commands devils: petitioners, other denizens of Hell and mercenaries who flocked to the banner of Hell all answer to him. Moloch runs a tight ship and suffers no insubordination, punishing transgressors harshly. Those who deliver on his expectations are rewarded accordingly, but he demands constant service. Moloch is a great tactician as well, having studied war in all of its forms for eons to become a true master. Desptie being the master of Malebolge he commands forces on the front lines, much like how Bel does it on Baator. This makes it seem that he and Barbatos have switched places when compared to their D&D kin. Moloch himself kind of looks like Bel as well, except he's combined with Deathwing; a giant burning dude with black metal that's also his skin and fire streaming between the gaps.

Baalzebul

The Lord of the Flies, Baalzebul was once the right hand man of Asmodeus. But he grew too proud, too greedy and this proved his downfall. When he demanded to rule over several layers of Hell instead of just one Asmodeus punished him by unmaking his beautiful angelic form and gave him a hideous one in return, much like how it went down in Baator. In Pathfinder however Baalzebul was turned into a swarm of millions of insects. When combined together these take a humanoid form that can sort of resemble his old body, except it's nowhere near as beautiful. Baalzebul is now plotting to get back what he lost and get revenge on Asmodeus. His arrogance and pettiness is to such a degree that while he favors the longsword he demands that his followers stick to spears instead.

Mephistopheles

Made from the very stuff of Hell itself, Mephistopheles is the ruler of Caina and the greatest master of the infernal contract to walk the planes. He loves to tempt mortals into giving up their souls, often without them realizing it. His favorite weapon is his adamantine quill pen that allows him to whip up a perfect contract in a few seconds. Mephistopheles has great skill at weaseling himself into the good graces of another person, figure out their secrets and force them to tell the truth. The devil himself looks like a classical horned and winged red devil, except he has three sets of wings: a pair of burning ones that can strike to set something on fire, a pair of draconic wings to make a target bleed and a pair of raven wings to make a target permanently go blind.

The Fiends of Pathfinder
Lawful: Asuras - Devils - Rakshasas - Velstracs
Neutral: Daemons - Divs - Sahkils
Chaotic: Demodands - Demons - Lilus - Nindorus - Qlippoth
Any: Oni
Lords: Ahriman - Archdevils
Demon Lords - Four Horsemen