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Also arguably Old Gregg's "Love games". He's not exactly a villain but then again there is what he did to Curly Jefferson...
And what he plans to do to poor Howard
Averted in ~It's Always Sunny in Philadelphia~ with the Nightman's cut song It's Nature, Shit Happens from "The Nightman Cometh. While the song is the Nightman's major piece, he spends it justifying his deeds by claiming to be evil by nature ("Some people are born evil with the eyes of a cat").
Super Sentai has a few examples: Himitsu Sentai Goranger has Akuma no Kurojuujigun, JAKQ Dengekitai has "Iron Claw's theme", Kousoku Sentai Turboranger has Oola no Urami, Kyoryu Sentai Zyuranger has Bandora's theme, "Dolla! Theme of Witch Bandora". And compare the opening theme to Gekisou Sentai Carranger (seen here) with the theme song to The Psycho Rangers of that series, Bousou Sentai Zokuranger (here).
Then there's Versti Fantur (Worst Villain) from one of the original LazyTown plays, which is arguably creepier and more sinister than it's remade counterpart "Master of Disguise".
The direct-to-video show The Adventures of Timmy the Tooth had the grinch-like Cavity Goon, who got his own song here (warning: low-quality video).
The Showa Kamen Riders have many. "Oh Shocker!" and "Akuma no Shocker" for the original, "Destron Sanka" for Kamen Rider V 3, "GOD(Government of Darkness)'s March", (Kamen Rider X) and "Wahhaha! Terrorizing The Country!" for Kamen Rider Stronger. The last two are done by Names to Know In Anime Koorogi '73.
Emmet Otter's Jug Band Christmas has the Riverbottom Nightmare Band singing an eponymous song. Lyrics include "We don't brush our teeth, 'cuz a toothache can help us stay mean" and "We break up your place / We are dangerous when we are near". The song actually fits into the plot because it is an entry in the local Talent Contest.
The short-lived Cop Rock had one song in particular called "Baby Merchant" that fit the bill.
While he's not technically a villain, the Janitor's verse in the middle of Dr. Cox's Rant Song certainly counts.
One Saturday Night Live "TV Funhouse" sketch had a fake preview for "Titey", a animated Titanic film produced by Disney. The villainous iceberg (voiced by Whoopi Goldberg) apparently gets her own villain song.
Ironically, Richard of Gloucester- infamously immortalized by Shakespeare as the arch-villain Richard III- gets a sweet, longing ballad in which he proves himself to have been quite a nice guy.