Darth Vader kicked this trope into high gear, to the point that he became the Series Mascot, inspired a slew of expies, and became one of the most beloved characters in pop culture, villain or otherwise.
There are only two things in The Phantom Menace that are, without debate, universally considered awesome: Duel of the Fates New World Symphony and Darth Maul. Both of which occur at the same time.
Boba Fett and moreso his father Jango, who get this for their distinctive voices and armor, to the point supplemental materials made up for their unimpressive film showings by giving them a large upgrade in badassery that permitted them the ability to take on Jedi and live.
Grand Moff Tarkin. There's only two people in the universe that can order Darth Vader around—the Emperor and Grand Moff Tarkin. And Tarkin's not even a Jedi nor a Sith of any kind. Taken Up to Eleven in Rogue One, where he expertly out-maneuvers Krennic at every turn and eventually blows him up with his own Death Star.
Director Krennic is this despite being almost the exact opposite of every other villain on this page, thanks to showing way more personality than most Imperial officers and his sheer quotability. The whitecape really helps, too.
Kylo Ren, especially in The Last Jedi. His debut appearance gives him a really cool suit, mask and lightsaber... but he also behaves like a wangstyEmo Teen throughout the movie and becomes a Hate Sink by killing Han Solo, his own father. In the sequel, he blossoms into one of the most complex and interesting villains in the saga; while still a childish, impulsive hothead, he becomes more deadly and competent as a fighter, overthrows his master Snoke as Supreme Leader, and reveals his unique motive of eradicating the existing duality of light vs. dark and Jedi vs. Sith.
Supreme Leader Snoke, who first appears as a three-story-tall hologram, has a menacing boomingvoice, and is played by nerd movie legend Andy Serkis. His awesomeness only increases in The Last Jedi, where he gains the below-mentioned Praetorian Guard, golden pimp-dud looking robes, and a thirty-seven mile-long flying wing as his flagship. He tosses his enemies and allies alike around with the Force like mere rag dolls, and also, unlike Palpatine, displays a wicked sense of humor and biting sarcasm, mocking Kylo Ren for his goofy-looking mask and smacking Rey with her own lightsaber. It's part of what makes it so genuinely shocking when Ren assassinates him.
Nines, aka "TR-8R", your average garden-variety Stormtrooper who took on a lightsaber user and won.
Dryden Vos is a straight example, being a massively intimidating, scarred, ultra-wealthy and violently unstable crime boss played by Paul Bettany to sinister perfection. Who wouldn't want to be an ultra-rich, pimp cape-wearing space mafia don riding around in a swanky, high-class yacht spaceship with his super-hot second-in-command/girlfriend and dealing with Imperial officers (and seemingly all other problems) via stabbing?
Clu's aforementioned Dragon, Rinzler. He has a cool outfit and mad fighting skills, and his being Tron himself not only makes him cooler, but also makes his HeelFace Turn and subsequent Heroic Sacrifice that much more poignant.
Legend (1985) thrives on this. People may complain that Tom Cruise isn't wearing pants and there's glitter on everything, but those horrifically cheesy lines the Lord of Darkness provides? Priceless.
Spider-Man: Norman Osborn fits this trope well. He was at coolest while talking to himself and wigging out. Being played by Willem Dafoe also helps out.
Spider-Man 2: Played perfectly straight. Doctor Octopus is made of win.
Subverted in a way when Peter Parker is possessed by the symbiote. He thinks he becomes this, but he is still noticeably our favorite geeky and clueless hero— he's just now arrogant and out of control. Though eventually he realizes that the symboiote is corrupting him and gets rid of the symbiote suit before more harm can be done. Furthermore, the symbiote eventually merges with Eddie Brock, who is noticeably slimy, unctuous, and creepy.
Harry Osborn gets this treatment in the 3rd film. Calmly rubbing a break up in your best friend's face is so wrong, but boy did Harry make it look cool. Especially while he is enjoying a pie. Plus this guy went through some of the worse beatings in the film and STILL survived most of them.
Darryl Revok of Scanners. Bad, bad dude. Pow. Michael Ironside always invokes this trope, whether its either Darkseid or Richter, even when playing a nominally good guy.
Applies to various evil monsters in the Godzilla movies, especially the Godzilla: Final Wars version of Gigan that gets chainsaw hands for the final battle. Also applies to Godzilla himself in the films where he is evil.
In The Lion, the Witch, and the Wardrobe, Queen Jadis in her bright attire out-cools almost all of her opponents on the battlefield, possible because actress Tilda Swinton is inherently cool in all her roles. She gets a war chariot pulled by polar bears!
In Prince Caspian, nasty uncle Miraz has some of the best lines (although it's hard to beat Edmund), thebest beard (not counting Aslan's), and probably the genuinely best set of armour. Miraz was less cool in the book, but the all-dialogue scene in the Howe with the hag and the werewolf was one of its most memorable bits, mostly due to the werewolf's creepy bragging. It ranks up there with Aslan growing delicious grapes for everyone and the duel.
Blood Feast is a great example of this. Fuad Ramses is the only good character in the whole movie.
The independent horror/comedy film Behind the Mask: The Rise of Leslie Vernon has the coolest new killer who looks up to Jason and Freddy, who lets a crew document his future reign of terror. Leslie Vernon is not only charming, witty, and genuinely friendly; before beginning his legacy, while in a library, he says, "Paradise Lost? Found it!" while grabbing John Milton's Paradise Lost. And he keeps turtles as pets and then tells the young woman interviewing him that he only kept pets that he could eat. His mask is amazing as well.
Avatar. Colonel. Miles. Motherfucking. Quaritch. Works out to stay strong on a planet with weaker gravity, commands a platoon of tough ex-armed forces mercenaries, rocks a customized mecha with a freakin' dragon painted on the gun barrel and a huge-ass combat knife, holds his breath, kicks down a door and steps into toxic air simply to pursue a traitor with his assault rifle, sports scary scars on one side of his face, and rides to battle in the Dragon Gunship while sipping fine Arabica Roast coffee. That he possesses the courage and determination to keep fighting no matter the odds merely adds to his Colonel Badass bona fides.
While the men of Gondor are just a bunch of unshaven men wearing plate mail, Sauron has not just his orcs and trolls, but the soldiers of Rhûn, spearmen with remotely creative looking armor and warchants that sound like the Haka, and the Haradim, who ride Mûmakil, which are essentially the ninety foot tall war elephants that Hannibal had wet dreams about. Their impact onto the frontlines of a charge from the Riders of Rohan (which had routed an orc army of dramatically superior size) was a moment where even the orchestra abandoned the forces of order as the Haradim rampaged through the helpless Riders until driven off by the Strong as They Need to Be protagonists.
Plus, Sauron's armour is ridiculously cool looking. Spikes everywhere, a huge, crownlike helmet that looks like a horse's skull, and the whole thing has a faint and delicate poison ivy motif etched into it.
Also, just as applicable, Saruman. It helps being played and voiced by Christopher Lee.
For a giant eyeball, Sauron is quite cool-looking himself. And then there's the Nazgûl.
Even though he was a minor bad guy, the Uruk-hai captain that popped up at the end of the first flick was also cool. He's one of the few characters that gets to smack Aragorn around a little, does a really cool Captain America-like shield throw, and has the audacity to shove Aragorn's sword into his gut the rest of the way with utter contempt and defiance.
The Balrog, who is probably the Boba Fett of the movies series: he's a One-Scene Wonder that takes out a major hero for the remainder of a movie and is one of the more memorable characters.
Keyser Soze of The Usual Suspects is clearly a monstrously evil man if even half of the things said about him are true, but his coolness in doing them is indisputable, particularly given the famous twist ending has made him a by-word for the Diabolical Mastermind.
Hans Landa from Inglourious Basterds. Despite being a Nazi officer, his intelligence, smooth and confident demeanor, and being a polyglot serve to make him probably the biggest Ensemble Dark Horse in the movie.
Many of the James Bond villains evoke this trope, and some have even been memorable.
Scarecrow from Batman Begins, who has an awesome answer to every problem that comes his way. Mob boss knows too much about his secret identity? Scarecrow pumps him with so much fear-gas that it drives him insane. The Batman shows up in his hideout? Scarecrow lights him on fire and kicks him out the window!
Rounding out the trilogy, The Dark Knight Rises introduces Bane. His appearance would suggest your typical dumb brute, but he's actually a Genius BruiserManipulative Bastard with a sympathetic backstory. He opens the movie by cutting a plane in half mid-flight and only proceeds to get more awesome from there. The first time he fights Batman is almost hilariously one-sided, he has a Cool Mask that makes his voice ominously low, and he completely takes over Gotham with minimal effort. He breaks Batman's spine (sort of) and sends him to a nigh-unescapable prison for several months.
Subverted with Roman and Minnie Castevet in Rosemary's Baby - the tackiest Satanists ever.
Gabriel from Constantine. Also, the Devil and Balthazar.
The Decepticons of the Transformers Film Series, as they usually are in most Transformers series. Case in point: the Autobots are limited by their desire to make Earth their second home, and must take on friendly appearances and altmodes to blend in with civilians. The Decepticons, on the other hand, have no such limitation. Therefore, they take on the forms of tanks, F-22s, and satellites, or, in the case of Megatron and Shockwave, simply reject reformatting their original forms. Additionally, they have access to numerous weapons, ranging from Transformer-sized fighter jets to a giant mechanical worm that serves as a war beast. Even the humans are aware of this, as Epps, at one point, asks to no one in particular "How come the Decepticons get all the good shit!?"
Megatron (as mentioned above) is possibly the best example of this among the 'Cons themselves, especially in the first movie where he's at his most Ax-Crazy and badass, and is easily the most interesting and entertaining of the robots in the movie, despite getting less screen time than the humans or Autobots. Oh, and he's voiced by Hugo Weaving (see above).
While Cats & Dogs gets flak from cat lovers for making all felines villainous, it does redeem itself a bit with this trope, with Mr Tinkles and his henchmen often claiming more amusing personalities and gags than the heroic dogs.
Terminator runs on this with the titular machines, so much so that the one played by Arnold Schwarzenegger got promoted to be a good guy in the second movie. In fact, Arnold hasn't physically played a bad guy note He lent his likeness to a CGI recreation of his face on a body double in Terminator Salvation since the first movie.
Predator, the titular villain proved to be far more remembered than the movie's heroes thanks to it being a badass that can Curb-Stomp BattleArnold Schwarzenegger in a fist fight in addition to its cool weapons and gadgets. Most of the Predators in the franchise have similarly followed suit with Wolf from the second Alien Vs Predator film being a notable example.
Alien: The Xenomorphs have a creepily fascinating design and Body Horror that makes them incredibly memorable. They're also super smart and come with frightening speed, stength, spiked tails and acid blood that make them incredibly hard to kill. These reasons alone have formed a large component of what has made the creatures such memorable villains in the pantheon of science fiction and film.
The Hellfire Club from X-Men: First Class. What else did you expect with villains that seem to have just stepped out of a Bond movie?
Ultron from Avengers: Age of Ultron, even more so than usual. Many found him a worthy successor to Loki, even more as Ultron actually fights the heroes by himself, is eight feet tall and sounds like a mixture of an ultra-snarky Tony Stark and Handsome Jack.
Adrian Toomes, a.k.a. The Vulture, from Spider-Man: Homecoming got this thanks to his complex and sympathetic characterization (a big change from the source material), a fantastic and creepy update on his costume, and Michael Keaton's memorable and menacing performance.
In-universe in Pacific Rim, where evil Kaiju are coming out of the ocean to kill humanity. The scientist Newt loves Kaiju, has tattoos of them on his arms, and even wants to see one up close some day. He's viewed by the others as a freak bordering on The Quisling. On one hand, 2500 ton giants with wings and knife-heads and acidic saliva and tentacle tails. On the other hand, murderous monsters. And eventually, he gets his wish. Twice.
Jurassic Park has the Velociraptors, which despite not remotely resembling their real counterparts, more than make up for it by being deviously cunning and ferocious man-sized lizard monsters. The T. Rex also counts when she's in a bad mood.
In-universe with the Indominus Rex of Jurassic World. This Mix And Match Critter mutant dinosaur was created by Masrani geneticists to replace good ol'Rexy as the biggest, baddest super-predator mascot of the park. Too bad she's also a psychopathic killing machine. This trope also applies to the Indominus itself, as it has all the best attributes of the T. Rex and Velociraptors rolled into one.
A good majority of slasher villains tend to fall into this due to the memorable designs and creative executions they come up with:
Freddy Krueger, who has his dream powers and razor claw glove. He's also notable for being one of the few slasher villains to speak, which helps contribute to his popularity due to his penchant for wisecracks. Helped even further by Robert Englund's magnificently iconic performance as the character.
Jason Voorhees, who has a sweet hockey mask, habit for large body counts in creative fashion and a large capacity for strength and durability. He eventually became a reviving zombie after being killed before upgrading into a robot. That's not even getting into the fact that he's gone up against armed cops and trained soldiers and taken them all out by himself with nothing but his bare hands and whatever he could get his hands on.
Child's Play: Chucky, due to his hilarious one liners, (Brad Dourif)'s extremely iconic performance as the character, his capability to be actually creepy, and his incredibly creative kills. His stitched up and scarred appearance in the later installments also help.
Barbarella: The Black Queen. She makes her debut by murdering two rapists that were about to assault our titular heroine, while wearing an Eyepatch of Power and showing phenomenal skill with two knives. She carries herself with flair and confidence even as her attempts to seduce Barbarella fail time and again. And it's her, not Barbarella, who puts a stop to the real Big Bad's plans, accepting that she will die in the process (due to sheer luck, she doesn't, happily enough).
Nothing but Trouble: Judge Valkenheiser is such an over the top combination of the Corrupt Hick and Hanging Judge that he's easily the most entertaining character in the movie, ruling Valkenvania like a king and executing people on a rock & roll rollercoaster that he built himself. Plus, while he's prone to levying disproportionately harsh sentences, some of his victims really did have it coming. Even the state troopers secretly love him!
Die Hard: Who wouldn't want to root for Hans Gruber?