TV Movie Special Award for portraying Coporate Power Mongers and Powerful Yet Seedy Government Officials - Robert Vaughn
Arthur Falconetti – Rich Man, Poor Man
Colonel Klink
Aunt Ester
Penquin
If you’re gonna count antagonists as villains, then throw in:
Mimi - Drew Carey Show
Serena - Bewitched
Gul Dukat “Deep Space Nine”
Mel & Susan Proffit, from Wiseguy
Kevin Spacey was spooky and Joan Severence was hot!
Alan Brady - Dick Van Dyke Show
Siegfreid - Get Smart
Don’t forget the schemers behind the villains!
Destro.
Starscream.
And of course, the Baroness.
The Monarch. Best henchmen ever.
Harcourt Fenton Mudd Star Trek: the Original Series
Que? 
The Riddler Batman. Frank Gorshin was superb in this role
The Joker Batman. Cesar Romero nearly as good as Gorshin.
Bob Twin Peaks. Scary as all getout
Leo Twin Peaks. He beat up on cute little Shelly.
Mr. Drysdale Beverly Hillbillies. Great line to his stepson- “You’ve never called me ‘dad’ before… don’t do it again!”
Jewel in the Crown - Ronald Merrick - fantastic villain
From the X Files:
Eugene Tooms - the mutant liver eater. Yikes.
Krychek - Heck, even I wanted to kick his ass.
And where would Seigfried be without Stalker.
Siefried: Stahlker, zis is Kaos, we do not pbpbpbpbpb here.
Simon Bar Sinister - Underdog
and in the category of best name…
Snidely Whiplash - Dudley Do-Right
Hank Scorpio from The Simpsons. Only one appearance, but man, he was fun.
Lex Luthor: Challenge of the Superfriends.
Good one! God, he was creepy!
Lucille I from Arrested Development. 
Frank Burns and Hotlips from MASH. (the first decade)
Ross Geller Friends
President Nixon The News