Several of the World Government's employees in One Piece follow this trope. Notable examples are CP9 and the Admiral Kizaru.
Crocodile commits all his devious schemes decked out in one of the pimpest don outfits of all time, hell, one of the first things he does after his arrest he gets a solid black even cooler version of the suit.
Doflamingo, given that he is not only a Shichibuksi but also the King of Dressrosa and it is implied he has connections with the World Nobles.
Light Yagami of Death Note usually wears a neat suit and tie, and is always impeccably groomed.
Lord Garygoyle from Nadia: The Secret of Blue Water also fits. His suite is immaculate red and worthy for the dinner party he invites sponsors too. The only flaw is his mask and KKK style hat
Sebastian from Black Butler. No matter what he's just done, he almost always shows up in an untarnished suit.
Ciel, too— perhaps moreso, as Sebastian's suit is technically his uniform, whereas Ciel's just a rich boy with opulent tastes.
Tyki Mikk from D.Gray-Man when he makes the effort.
Used a lot in Tiger Mask: the usual attire of Tiger's Cave wrestlers for public non-fight apparitions is an expensive suit and the mask, Tiger's Cave admins wear nice suits and a Ku Klux Klan-like mask, Mr. X almost constantly wears an expensive shirt, tuxedo and top hat suit complete with a golden ring with a tiger's head (the exceptions being when refereeing the World Maskmen League, when he discarded the tuxedo and top hat while on the ring, and a travel attire he wore twice while trying to pass unnoticed), the anime-only supreme admin almost always wears a nice white suit (even if never with the mask), and many heel wrestlers outside of the ring wear expensive clothes of good taste. Played with by the protagonist: while his out-of-the-ring attire as Tiger Mask is composed by the same suit of the admins, the mask and a tiger-striped cloak, he's quickly revealed as an Anti-Hero.
Black Joke is full of them, since the series is all about fabulously rich criminal organizations fighting each other.
The Joker, depending on the incarnation, wears a tuxedo. Alex Ross's version of the character wears a black tux (no purple) and a white bow tie with spats and a cane. In fact he quite often wears tails, which constitute "white tie" and thus out-formal a tuxedo (black tie), but since he often wears his tails before 5 pm he's obviously a bounder of no breeding.
Most Batman villains at one time or another wore a suit or tuxedo.
Marvel Universe: The Kingpin only wears personally tailored designer suits. Of course, given his size, his suits would probably have to be custom made regardless of the quality.
In his Corrupt Corporate Executive days, Lex Luthor would almost always wear a black or gray business suit. In fact, in the DCU, the "Luthor Look": a black suit and shaved head, became the preferred style for CEO's.
Vandal Savage is usually shown wearing expensive suits. In fact, he probably invented them.
Lucifer. Throughout his series he usually wears a sharp white suit.
Star Wars: Count Dooku prides himself upon elegance, refinement, and dressing to suit his rank (which, incidentally, is not self-granted; he really is a Count).
Some James Bond villains fall into this trope. Subverted(?) since our James is a pretty sharp dresser himself. Subverted even more strongly in the books, where Bond (who dresses sharp, but subtle) often notes the fabulously expensive outfits the villains are wearing are also terribly flashy, garish, and a sign of "trying too hard".
At the end of Interview With A Vampire, Lestat plays "Sympathy For The Devil" on a car radio. Granted he went out of style a few centuries ago and isn't looking his best, but he's still Lestat.
Lestat is a fashionista in the novels, and was even as a human, as soon as he got his Badass Cape (and boots). He always prided himself on being impeccably dressed in the most stylish fashions of the day, insisted whomever was in his care was also suitably dressed (Claudia, and later Satan's Night Out), and more often than not seemed to pick his victims for their wardrobes as much as for their villainy. Any time the text is written from Lestat's point of view, you can bet there will be at least one paragraph reminding the reader what he's wearing.
Hans Gruber in Die Hard: "Nice suit... John Phillips, London. I have two myself. Rumor has it Arafat buys his there."
Shiwan Khan: In three days, the entire world will hear my roar, and willingly fall subject to the lost empire of Shan Kahn. That is a lovely tie, by the way. May I ask where you acquire it? Lamont Cranston: Brooks Brothers. Shiwan Khan: Is that mid-town? Lamont Cranston: 45th and Madison. You are a barbarian. Shiwan Khan: Thank you. We both are.
Incidentally, the next time Cranston catches up with Khan (having dinner at a restaurant) the villain has acquired himself a suit and tie. It doesn't suit him (no pun intended).
Lucifer in Constantine wears a white suit, buth without shoes and black tar dripping from his bare ankles. Personal hygiene apparently isn't a big deal when you're the Prince of Darkness.
The demon played by Gavin Rossdale and the angel played by Jadis also wear some wicked suits, at least until the end where the angel Gabriel is apparently an escaped mental patient reduced to some nice pants and a wifebeater/corset.
The Dark Knight - Averted. The Joker wears the shoddiest clothing imaginable, but it's pretty clear he's an evil, evil man.
It may have been a nice suit at first, but it's obvious that the Joker isn't too big on upkeep. He mentions that the outfit wasn't cheap, being paid for by Gotham's stolen mob money and all. It's also mentioned by the police to be custom-tailored after his arrest.
Ra's al Ghul and Scarecrow from Batman Begins and Two-Face from the sequel play this trope straight.
Bedazzled (1967), the 1967 version — the Devil, when he's not dressed for evil work (as a telephone lineman, beekeeper, scuba gear drilling holes in oil tankers, etc) wears a tuxedo, cape, and cool mod sunglasses - and red socks with whatever else he's wearing.
If Shaffer's Amadeus's Salieri counts as a villain, then he truly was a Man of Wealth and Taste- pun intended.
Patrick Bateman in American Psycho puts a great deal of importance on clothing, suits and fashion. He is careful to don a plastic raincoat before killing Paul Allen so he doesn't get blood on his suit.
Mob boss Top Dollar from the movie adaptation of The Crow wears very fancy, expensive vintage clothing and keeps an array of antique swords nearby. This contrasts with his mooks who all dress in average clothing (jeans, jackets, etc.).
In Drive Angry, the demon sent after Nicolas Cage's character, known as the Accountant (played by William Fichtner), wears a black suit that never tarnishes. He can crash in a car off a bridge and walk out dressed impeccably, without a single crease.
Lee Woo-Jin, the antagonist of Oldboy. The final confrontation happens just after he had a shower, which means we are treated to the Man Of Wealth And Taste's version of a Lock and Load Montage, including loving close-ups of his tie clip, his cufflinks, his shoelaces...
The Emperor from Curse of the Golden Flower's presence is often announced by the jangle of one of his splendid golden suits (oh yeah, and a servant yelling "his majesty the Emperor arrives!") Justified of course by him being the Emperor of China!
Sebastian Shaw in X-Men: First Class is Faux Affably Evil and always wears stylish clothes (with the exception of his anti-telepathy helmet), camouflages his submarine under a luxury yacht, and serves excellent champagne to the officials he's trying to manipulate into causing World War III.
Woland of The Master and Margarita: throughout most of the book, he appears as a wealthy, educated, and flamboyantly dressed foreigner. He's also Satan, so evil comes naturally, although whether his actions are for good or ill constitutes a debate unto itself.
Most of the Imperial officers in the Star Wars Expanded Universe wear the same sort of uniforms as they do in the movies, and they are pretty much stock evil. Grand Admiral Thrawn wears white, and he is extremely cultured and, while still villainous, visibly more ambiguous. He's also an alien, and actually all the Grand Admirals have white uniforms. It's just that none of them are nearly as prominent, having all been either killed or captured years earlier.
When "The Man", a very suave Horny Devil, first showed up in flashback stories in his pinstriped suit and natty hat, the above lyric got quoted by a reader in the chapter comments.
Vice-Chancellor Embries, appearing human but in reality a shapeshifting greater dragon with a penchant for eating his secretaries, is always impeccably dressed.
Here's a fun Drinking Game: take a shot for each of Shakespeare's "gentlemen" who are liars, traitors, thieves, or just general cads. Each and every of them was dressed in the height of fashion for their time and place.
Gentleman Johnny Marcone, wears suits that cost more than Harry's car and once managed to throw a concealed knife through a rope holding him up while hanging upside down and spinning around while a bloodthirsty loup-garou was about ready to try to eat him. In the dark. He's an Anti-Villain who ends up in Enemy Mine situations with the heroes a lot, but he's still not exactly a nice guy. He is, however, composed of pure, solidified Badass Normal.
Lara Raith is also a pretty snappy dresser. Presumably she gets this from her father.
Cosmo Lavish in Making Money tries to pull this off (in imitation of Vetinari, who isn't exactly evil) and completely fails due to being morbidly obese.
Every single Assassin. After all, if one isn't impeccably dressed in the latest black silk, one might as well be a common thug who kills people for money.
Maladict, a vampire, manages a variant of this trope while in the army, by wearing the uniform so it's "deshabillé [...] scruffy, but with bags and bags of style".
Lord Hong in Interesting Times, who, in addition to being a very well-dressed Agatean nobleman, has a very expensive suit of Western Sto Plains clothes for when he conquers Ankh-Morpork, complete with silk-lined cloak and a Nice Hat with a feather in it.
He would walk through the city on that first great day, and the people would be silent when they saw their natural leader. It never crossed his mind that anyone would say "'Ere, wot a toff! 'Eave 'arf a brick at 'im!"
Crowley and "Dr. Raven Sable" (Famine) in Good Omens.
Patrick Bateman's love of suits and fashion, as mentioned in Film, is given considerably more screentime (so to speak) in the book: every outfit is described in great and loving detail, down to brand name, fabric, and cut.
In The Guardians, this is the form demons take to live among humans and tempt them into evil; at least one is a US Senator. Subverted when the Guardians can't find a demon and later realize it's taken the form of a womanof wealth and taste.
Lucius Malfoy from Harry Potter, as befitting the patriarch of a very old and prestigious wizard family.
Not quite as evil, but also somewhat ethically challenged and narcissistic, is Gilderoy Lockhart, who relied on questionable means to advance his career.
Philonecron of the Cronus Chronicles series. He wears a victorian-style suit and a long cape, and frequently insults humans on their "atrocious" fashion sense. He even bought very high-quality tuxedos for all of his evil henchmen.
The Vampire Chronicles: Lestat insists on being at the very height of fashion wherever he goes. Whether he's in a frock coat, three-piece business suit, Badass Cape, or jeans and t-shirt, everything is of the highest quality and selected to convey the image Lestat wants to impart. Interestingly, Lestat seems to have an almost Cloud Cuckoo Lander-like attitude towards his wardrobe, veering wildly between disinterested and obsessive. Clothes that he gets dirty will often be shoved in the bottom dresser drawer and never thought of again, while he showers adoring affection for an old woman who knows the story behind the themed cameo-image buttons on the jacket he's wearing. He plays with a Refuge in Audacity approach in Blood Canticle when he and his latest proteges "invade" a remote Caribbean island: They could easily sneak in through the heavy jungle, or just use their powers and slaughter everyone between them and the information they're seeking, but Lestat instead decides to garb his coterie in the most outlandishly over-the-top outfits in their wardrobes and dazzle their way past the drug lords in residence: The young man with him dresses in a metallic gold three-piece suit, the young woman in a high-hemmed ostrich feather dress not out of place in the Roaring 20's, and himself in a full leather suit described in the book at least a half dozen times, because he likes it that damn much.
British statesman Lord Chesterfield disputed this trope in Letters to His Son: "I have often known a fashionable man have some one vice; but I never in my life knew a vicious man a fashionable man." (letter 77)
All of Wolfram and Hart from Angel. Particularly Holland Manners - wine cellar, trophy wife - and Lilah Morgan - next spring's Boracchi. And Hamilton, who can engage in any amount of Bad Ass fighting without ruining his suit. Everybody even comments on how well-dressed Hamilton is during his debut episode.
Also Darla, who favors apartments with view. And Angelus, who was always coiffed in the old days. And Spike and Drusilla. Then again, they're vampires.
The Master on Doctor Who, depending on who's portraying him. Roger Delgado and John Simm's Masters frequently wore great suits, Anthony Ainley's Master wore suits a few times, and Derek Jacobi's Master wears a Victorian version.
The Goa'uld in Stargate SG-1 tend to go for the traditional A God Am I-style flowing robes, headdresses, and gold ornamentation everywhere. The Affably Evil Baal, however, prefers a stylish turtleneck-and-suit-jacket combo - especially when he's pretending to be the CEO of a major Earth corporation. The fact that he's the only Goa'uld who remembers that he's only pretending to be a god probably has a lot to do with this.
Notably, the Devil from Reaper is always seen wearing his trademark suit (of which he has multiple copies), and even has a subplot where his tailor dies, leaving him at a loss with what to wear.
He always looks cheerful too. At one point he expresses his disappointment in Sam by dropping store shelves on him. It's probably not a good idea to get him angry.
Jack Bass on Gossip Girl. Bart and Chuck could also count.
In the Burn Notice episode "Friendly Fire", Michael coerces the allegiance of a gang by Wearing a red and gray silk suit, talking like Clint Eastwood and blowing things up by snapping his fingers.
Ashes to Ashes. Big Bad Superintendant Mackintosh favors well-tailored suits, but the real Man Of Wealth And Taste is Jim Keats, with his monochrome grey suits and black leather gloves.
Sherlock's Moriarty is finally introduced wearing a very fine suit.
Subverted by his first appearance as the obviously gay "Jim from IT", going so far as to leave Sherlock his number.
In the short-lived Brimstone series, The Devil (played by Lionel Luthor) wears an expensive Victorian suit, complete with a red tie and a pocketwatch. In contrast, an angel is shown looking exactly like him but dressed as a blue-collar worker (a ceiling painter).
It can be debated whether or not King Silas of Kings is evil. It cannot be debated that he has excellent taste in suits.
In Once Upon a Time, while Rumplestiskin was slimy and grimy in the fairy tale world, he arranged things so that he would be a man of substance in the Storybrooke world, and so as Mr. Gold, he always wears snazzy, finely tailored suits and generally carries around a gold-topped cane. In both worlds, he's your go-to guide for making a Deal with the Devil.
When he was playing the heel, Alberto Del Rio would often show up in expensive cars with a gold scarf and a nice suit, claiming that all of his lavish trappings were things he was "destined" to have. This is dropped when he's face, instead playing on his proud Mexican heritage.
Practically the first thing Mephistopheles does in Faust is call attention to his elegant, fashionable attire.
Also subverted by Zinc Lablanc in Ace Attorney Investigations: Miles Edgeworth; despite the name of his Leitmotif being Man Of Wealth And Taste, his outfit is incredibly gaudy, to the point of being worse than Redd's. The only thing Lablanc's really got going for him is that he doesn't have ridiculously-colored hair (blond, as opposed to purple). Also he's not evil. Just annoying.
Kristoph Gavin, a murderer from the fourth game, wears a pretty neat double-breasted suit.
Manfred von Karma might fill this trope... in the seventeenth century. Cravats have fallen out of fashion nowadays. (Don't tell Edgeworth that, though.)
Pokey begins wearing a suit after becoming Monotoli's right-hand man in EarthBound.
Vampires in The Sims 2: Nightlife. The Counts wear Bela Lugosi knockoff suits with tailcoats and such, the Contessas wear old-fashioned evening gowns with puffed sleeves and lots of gold embroidery.
Vergil, as seen in Devil May Cry 3, wears a more old-timey outfit, complete with ascot, compared to Dante's modern fashion sense. Then again, he is an Anti-Villain rather than all-out evil. The human form of their father Sparda wore even more old-timey, complete with elaborate cravat, but he was a Defector from Decadence. Dante's lack of this has been theorised by some as symbolic of his estrangement from his family, which may make his case a Defied Trope.
Tekken: Kazuya Mishima, Heihachi Mishima, Lee Chaolan and Jin Kazama all have incredibly dressy outfits for a fighting game; unsurprisingly they're all part of the same family. It remains to be seen if Lars will follow suit.
The Illusive Man in Mass Effect 2 prefers to do his meetings reclining in a chair in front of an impressive vista, wearing an impeccable suit, a cigarette in hand and a glass of expensive bourbon nearby.
Donovan Hock and Elias Kelham are lesser examples.
Cardinal Albert Simon from the Shadow Hearts series is dressed impeccably, wearing a very neat black suit, Waistcoat of Style, pocket watch, and tall top hat (the game being set in 1913, it's thematic). Being a Well-Intentioned Extremist, one might say it's either subverted or played straight.
Nor can one say it about the good in Symphony. Alucard is every bit a snappy dresser as his old man.
Hitman: Agent 47 is rarely seen without his all-black suit with matching leather gloves and distinctive blood-red tie. A number of other rival assassins and targets are seen wearing expensive suits as well.
Shang Tsung of Mortal Kombat certainly qualifies as this, from his outfits to his secluded island to even his palace. While Goro's lair is dark, dirty and covered in blood, skeletons and debris, his palace has pure opulence, from velvet curtains to golden dragon statues to his throne.
Vampire: The Masquerade is full of them. Clan Ventrue is probably the most notable, as their clan hat is noble bearing and financial acumen, but many examples can also be found among the Lasombra, Tzimisce, Toreador, and Giovanni.
Giovanni Villanova from 7th Sea is an archetypal example of this trope. He's evil with a capital E, has a prison built to spec as his own private hell for his enemies, beats his "fate witch" wife, and is generally despicable to the Nth degree... but he's a Prince, by Deus, and that means showing some style. One iconic moment is when he knifes a man from behind (one who's threatening the PCs), shoves him aside... and starts eating the victim's Fettucine Alfredo, because it's too good to waste. He also laments having the cook killed, because the pasta's that good...but while it's one thing to poison an enemy, it's another entirely for the cook to poison such works of art, so he had his men feeding said cook his own poison. Even Evil Has Standards, after all.
White Wolf offered an interesting justification in a short vignette written from Lucifer's perspective in Demon The Fallen. He can't feel pleasure, or happiness, or anything good... but the bad stuff? He can feel the bad stuff. Every scratch of the fabric, every slight pain from an ill-fitting piece of clothing, every pang of hunger. He travels in utmost luxury, wears the best clothes and eats the finest food just so he can get as close as possible to feeling nothing.
While not a suit, Asmodeus from Dungeons & Dragons wears "regal finery of unimaginable expense", said to cost as much as a country spends on food in a year.
The version of Satan from College Roomies from Hell!!! often introduces himself with the trope title, but has never shown much sign of actually living up to it. Hazel Green fits the trope better, albeit as a female example.
Whateley Universe example: unstoppable assassin cyborg Deathlist wears an expensive pinstripe suit when he and a small army of bad guys invade Whateley Academy. Everyone else is in military gear or armor.
An essential feature of Lex Luthor in Superman: The Animated Series. He always was seen in black coat and slacks, with a white vest and tie. In his last appearance, in Justice League Unlimited, he even remarks that to properly deal with Darkseid, he has to get into his "power suit", abandoning the khaki uniform he had been wearing for his original garb.
His appearance in Young Justice also counts. Vandal Savage and Count Vertigo also fit the bill.
Justice League Unlimited: Vandal Savage always wears a nice suit or a nice uniform, when he hasn't had a castle dropped on him.
Metalocalypse - the band is in the Deep South learning the blues, which involves going to the crossroads to sell their souls to the Blues Devil, who is a gaunt, scary-looking man with a milky white eye and a sharp suit and hat.