Now, the bronies make extremely good music as a matter of daily life, but Nightmare Moon's fan-made Villain Song, "The Moon Rises" will blow your mind and leave you shaking in your shoes. Written, composed and performed single-handedly by the amazing Ponyphonic.
There's also Avada Kedavra as sung by Voldemort, Wormtail and Draco Malfoy. It was made by "Albino Blacksheep" and "Too Much Spare Time Animation" and parodies The Lion King's Hakuna Matata.
The song was actually made by a band named Nuclear Bubble Wrap, sung by the two main singers Jace McLain and Kyle Thorne, with guest singer Steve Goodie as Voldemort. And by God was that the right choice.
Though because Dr. Horrible is a Villain Protagonist, (and at least three of his songs describe his villainous motives), this trope is probably better exemplified by Captain Hammer's Everyone's a Hero in Their Own Way near the end of the film, which demonstrates he's a complete jerk while superficially sounding heroic.
Everyone's a hero in their own way Everyone has villains they must face They're not as cool as mine But folks, you know it's fine To know your place...
Given how unnecessarily brutal he is to Doctor Horrible (he could probably have stopped him without grabbing him by the neck and slamming his head into a van or throwing a car at his head) and the fact that he tries to murder Dr. Horrible in the end (granted, Horrible intended to murder him first, but two wrongs don't make a right), one could perhaps argue that Hammer is also a villain anyway. That would make Everyone's A Hero a straighter example of this trope and A Man's Gotta Do an unusual case of a villain song started by one villain and then hijacked by an opposing villain (since Horrible starts it and Hammer takes over).
And the two versions of the Bad Horse Chorus.
It can be argued that every song in Dr. Horrible's Singalong Blog is a Villain Song except for 'Caring Hands' and 'Penny's Song' (both of them being sung by Penny). 'My Freeze Ray' is somewhat on the ropes, it's more about love, but it has it's more sinister lines, plus it's sung by the anti-villain anyways. So They Say is similar in that the majority of it isn't evil, though Captain Hammer and Dr. Horrible both have lines in the song.
Played with in New Kids On The Rock's Ryan's Christmas Wish: The Large Ham villain The Misery Meister gets his own jaunty alliteration-filled villain song (which occurs about 11:51 into this video), but the flashiness is limited to intentionally stiff dancing, tossing rag dolls around, and menacingly wielding a small meat grinder, and after a verse we flash forward two minutes later to the very ending of the song.
A Very Potter Musical has the upbeat, show-stopping "Dance Again", in which a newly reborn, shirtless, sexy Voldemort tap dances and leads a deatheater kickline. Voldemort and Quirrel also have the duet "Different As Can Be" where they sing about what an Odd Couple they are as a pair of villains, and a cheerful reprise after they've done some serious bonding.
In "Get Back To Hogwarts", Draco's verse is about how he's going to replace Harry as the most popular kid in school. Not exactly villainous, but still antagonistic.
Someone created a Filk Song of Magneto and Xavier singing Defying Gravity from Wicked, in which Magneto abandons Xavier's plans for peaceful coexistence with humans. It's somewhere between this trope and an "I Want" Song. Quite awesome.
Edward's song in Twilight The Musical with the notable line "I'll show you anaphase when I rip you in two." Way better than the actual Edward!
Film Cow's "Make Me Smile", sung by a psychotic anthropomorphic ferret definitely counts. It's a cheerful, jaunty tune that features holocaust denial, a pro eugenics attitude, molestation, murder and cannibalism. It's absolutely hilarious.
An unrelated musical adaptation of the same name on reverbnation.com gives three songs for Dr. Heiter: "The Pieces are in Place" when he has all three of his test subjects together, "Putting it Together" when he constructs his human centipede, and "Dieter Sings Some Shit About a Gun" when he is confronted by the police and ponders what to do.
In Pony Dot Mov, Fluttershy constantly tells the other characters to stay out of her shed. When some of the characters don't heed this, she revs up a chainsaw and prepares to punish them by singing "Gonna Eatcha Brains". For the record, it's sung to the tune of the Fat Albert theme song.
