The sequels of The Land Before Time have a few: You got When You're Big, sung by a trio of teenage dinosaurs who are bullies towards the heroes, Eggs, sung by a pair of dinosaurs, singing about their obvious addictions, Who Needs You, sung by a pair of incompatible villains (essentially a bird and an alligator) about how they don't need each other, and Very Important Creature, sung by an egotistical Pteranodon.
"Playing With the Big Boys Now", sung by the High Priests of Ra in The Prince of Egypt. Although these two are more like lackeys to the main antagonist of the story, they certainly have all the flair and menace of a good villain song. It sounds especially strong in Greek.
The Pharaoh's part in "Plagues" counts as well. "Then let my heart be hardened/ and never mind how high the cost may grow/ this will still be so/ I will never let your people go!"
The rest of "The Plagues" actually has many features of a Villain Song, only it's being sung by God. It's something of a response to "Playing With The Big Boys Now" which preceded it.
"Big and Loud" sung by Darla Dimple in Cats Don't Dance. Part one is used to deceive the protagonist, and part two is Darla's gloating monologue about her success and the unpleasant future in store for the heroes. Like any good animated villain song, the visuals are over-the-top spectacular.
The Rankin-Bass animated version of The Return of the King features a song, "Where there's a Whip There's a Way", sung by orcs. While this is one of the coolest song titles EVAR, it's still just plain wrong. It's arguably the stand-out number, although it's hard to compete with Glenn Yarborough singing Sam and Frodo to sleep on Mount Doom or with a number where Sam fantasizes about how if he had the Ring he would use its powers to turn the orcs and baddies into regular critters like raccoons and porcupines.note Loosely based on a scene from the book!
Sounds more like a Villainous Lament. "We don't want to go to war today" and "we are the slaves of the dark lords' war"... (Ironically this may be close to Tolkien's view that the Orcs aren't fully evil, just forced into it.)
Easily the worst villain song is the Villain song by Marvin McNasty from Pound Puppies and The Legend of Big Paw. It's just him screaming a bad parody of 'Hoochie Coochie Man'. Then a random Jazz Elvis thing happens, tears of hysteria rolled down from the viewer's eyes at how bad it is.
Dude, Lou Reed probably begged for it, what worthy rock star would pass up the chance to be the biggest thing since world war three?
Of course, Shrek subverts it every way it can. The main villain of Shrek 2 gets not one, but two songs: The first one is the self-titled "Fairy Godmother Song", a cheerful upbeat ditty about how she wants to help everyone; the second comes complete with an ominous orchestra and backing choir... except the song in question is "Holding Out for a Hero".
There's a reason it was that song, considering it's the background music for some dramatic heroics from Shrek, Donkey, and Puss.
Played straight in the Broadway musical, which gives Lord Farquaad two songs: "What's Up Duloc?", where he sings about his plans to conform the kingdom to his ideals, and "The Ballad of Farquaad", where he sings about the turbulent relationship with his father and his mother's death that led to where he is. Of course, being Shrek, it was all very tongue-in-cheek: turns out Daddy was Grumpy.
"Who is the Boss?" from Felix the Cat: The Movie. Not sung by the villain himself, but it's sung to praise how much of a powerful man the Duke of Zill is. Plus he introduces the song by saying a few interesting lines. Have your fun, as long as I let you have fun!
The Titans from The Xena/Hercules Animated joint had their own song about how they where gonna get revenge and cause chaos and how they were "the best". It's even annoying to characters IN the film!
A VeggieTales movie, one about Daniel and the Lion's Den, where the wisemen (played by three Scallions) sing a song called "Oh No! What We Gonna Do?" where they plot Daniel's downfall. Their techniques get sillier as they go on, and they're soon talking about using him as a "table to play Scrabble on" which leads into a great rhyme of Babylon.
Then there's "The Bunny Song" in "Rack, Shack, and Benny", about idolizing a chocolate rabbit. This one caused a lot of controversy, and the creators use a rewritten version of the song on CDs and sing-along tapes. Amusingly, the back up singers have the same verses, with the main baddie scolding them and warning that they'll get tummy aches..
The French Peas taunt the Hebrews in the desert with the catchy "Keep Walking" in "Josh and the Big Wall."
In "Esther, the Girl Who Would be Queen", Haman sings to the king about the supposed threat of the Jews in a surprisingly dark song.
Ruber gets a self-titled song in Quest for Camelot where he proclaims Camelot as his while standing behind a glowing green pit. During the song he throws his minions and weapons into the pit, combining them into partially metallic monsters with weapons for hands.
Balto 2 has The Grand Design for Niju, well, sort of. Niju and Nava are the lead singers and Niju has most of the lines. His lines are also quite villainous in nature, showing his motivation, so it qualifies.
The Good, The Bad, and The Huckleberry Hound has "Gold, Gold, Gold" performed by the Dalton Brothers.