The Fallout series has many, many evil people, but Dr. Stanislaus Braun really takes the cake. He is found inside a virtual reality simulation, having been the sole administrator for 200 years. What has he been doing all this time? Why, torturing and killing the others in the simulation over and over again of course! He specifically mentions that doing so is only fun because they are real people, and not computer simulations.
Roy Phillips. If the Lone Wanderer negotiates with Tenpenny and his tenants to let the ghouls move in, eventually, upon returning to Tenpenny Tower, all the human residents have vanished. If you check the basement, you'll find the corpses of the missing people stripped of all their possessions. Even poor Herbert Dashwood, who supported ghoul equality, is among the dead. If confronted, Roy tells you to fuck off before he adds you to the pile.
The third installment also gives us the Talon Company, which has no apparent redeeming qualities. Every last member is a Psycho for Hire.
In Fallout 2, three of the four New Reno families fall under this category. Wright is considered the "good" family.
Also from Fallout 2, Myron. He developed the highly addictive and dangerous drug "Jet" for the Mordinos in exchange for money and whores. How did he develop said drug? He conducted experiments on around a hundred slaves suffering from heart conditions, resulting in death by cardiac arrest for nearly all of them until he got the recipe right. If you call him out on this, he'll openly wonder why you care about the lives of the slaves anyway. He even takes pride in how many lives his drug has ruined, and will never stop bragging about it. Fortunately, in the epilogue, he gets one of the most appropriate Karmic Deaths in the history of fiction.
Fallout: New Vegas: Cook-Cook of the fiends. The fiends themselves are choatic Jerkass types who torture people for fun, but Cook-Cook is so bad that he is barely tolerated by even the other fiends. He alternates between burning people alive, cooking (quite well apparantly), and rape. Two Westsiders, who made a profit kidnapping refugees and selling them to just about everyone (and stopped raping them because it lowered their value), were squicked when this guy didn't even wait for them to turn around before enjoying a family he brought them, starting with their son. One time, he bought some teenage slaves, 3 girls and a boy. The boy was burned alive and the girls made to watch. To say nothing of his implied cannibalism and what this could further implicate about that incident...........
The Omertas, with the exception of Cachino. Their leadership is secretly working for Caesar's Legion to massacre the entire population in New Vegas as soon as the battle at Hoover Dam begins. But Cachino knows something serious is up with the Omerta bosses and will even help you ruin their plans to help the Legion chlorine bomb New Vegas.
Big Sal: Caesar asked us to provide a distraction on the Strip. So when he gives the word we're going to launch an all out assault on the Strip. First we're going to blow the embassy, then we're going to use soldiers to kill every last motherfucker on the Strip. Then we'll run this joint. That'll teach Not-At-Home what can go on while he sits in his fucking ivory tower lording down from on high.
Special mention must go to their man Clanden. He seems perfectly friendly enough, but then you can find a locked room close to his suite where there's a dead hooker, who, if you have a high enough medicine skill, is revealed to have been tortured to death. And, you can get into the hidden safe in his suite, you can find a holotape that is described to "contain horrific sounds of murder and violence. You hear Clanden engaging in violent sex with women, and then hear the sounds of visceral and violent murder being carried out." Thankfully, it's only a description and you can't actually play a recording of what's going on.
The Enclave in the first two games were definitely this. First of all, all of those utterly horrific Vault Experiments? They were behind every single one of them. That's right; Vault 11? They did it. Vault 112? They did it. Vault 97? You get the idea. Their first onscreen action in the series is to massacre a whole vault full of innocent men, women and children, just because some of them had a trace of radiation in them. That's right, they are so obsessed with rebuilding a "pure" America that they are willing to commit genocide on not just Ghouls and Mutants, but literally anyone with even the smallest bit of radiation in them. That's over 90% of America's remaining population. They don't care. Among the worst is Fallout 2's Agent Horrigan, who is best described as a "genetically engineered cyborg psycho total homicidal maniac." He always murders someone whenever he appears, the first victims being a group of unarmed peasants.
The worst part about the Enclave being behind the Vaults? Everything the public had known about them was a complete and utter lie. They were never meant to save anyone.
Father Elijah from Dead Money. He was the former elder of the Mojave Wasteland Brotherhood of Steel, and the one responsible for them all getting slaughtered at HELIOS. He fled from the battle and eventually reached a fortress of technology called the "Sierra Madre". However, to access the technology he needed, he had to go through a bunch of defenses like laser turrets, invincible holograms, a big cloud of poisonous gas appropriately refered to as "The Cloud", and an army of Ghost People. So what does he do? Go through it himself? No, he enslaves a nightkin named "Dog"(who is severely mentally impaired, even by nightkin standards, to the point that he has developed a seperate personality known as "God"), and proceeds to force him to kidnap dozens of people to act as cannon fodder for the security of the Sierra Madre, threatening to blow their heads off with his slave collars if they tried to escape (and if the headless corpses by the entrance are any indication, he did just that several times). He then captures you, and he forces you through all the same things as others, except he gives you the help of a team of the other people he captured. You surprise him and eventually reach the Sierra Madre casino, where all this tech he is looking for is located. So then what does he do? He orders you to kill off your former team, simply because they are of no use to him anymore. When you've done that (or haven't, and simply convinced them to leave), you reach what he was looking for: The Sierra Madre vault, and it is here that he reveals his true plan: To unleash the Cloud upon the Mojave, killing every single person there (or "wipe the slate clean", as he calls it), then using the invincible holograms and the other tech to build a new nation, a new nation where everyone has a slave collar slapped on them, so they won't think if disobeying him. Then, to finish off his grand plan, he tries to kill you, despite your loyal service to him. Needless to say, blowing his head off or locking him in the Sierra Madre vault until he starves to death is very, very satisfying.
Salt-Upon-Wounds, the leader of the White Legs from the DLC Honest Hearts. He and his tribe of powerful warriors really wanted to join the Legion. The Legion agreed to let them in, but they had to accomplish one task first: destroy the peaceful town of New Canaan. How did Salt-Upon-Wounds and his warriors go about this? They burned the surrounding communities to the ground, took advantage of the New Canaanites kindness to get them to let the White Legs into the town (since they couldn't take the New Canannites in a straight up fight) while pretending they were refugees, then they killed everyone there. The old and sick were butchered as they tried to leave. Priests were burned alive in churches. The children were beaten to death with clubs as they slept. Once you figure out about all this, it's really difficult not to take the "Crush The White Legs" option and kill every last one of these bastards, Salt-Upon-Wounds included.
Also he waited to do this while most of New Canaanites who could fight back were out, inclucing the person they were order to kill! In fact he was the only one they really needed to kill.
Mr. Burke in Fallout 3. His boss, Allistair Tenpenny, sent him off to set off Megaton's undetonated nuke after evacuating the town and the immediate area of people (not exactly a saintly thing to do on Tenpenny's part, but he at least wanted to avoid killing people). Burke, however, decided to ignore the "evacuate the people" part and was planning on just nuking the town with the innocent people still there.
Werner from The Pitt. All his talk about being a slave freedom fighter is a lie. He's really a disgustingly selfish Manipulative Bastard whose sole concern is taking control of the city from the much more fairminded Ashur. He views his fellow slaves as little more than pawns to move around in his quest for power. Oh, and he knows full well that the Trogg cure is really Ashur's infant daughter, but he doesn't care. If he has to kidnap and quite possibly torture an innocent child just to rule one city, he's exactly as monstrous to do it. In summary, Wernher literally cares for nothing but himself, and is willing to lie to and kill anyone who gets between him and his selfish goals.