A gots a list. ^^
Il Palazzo (Excel Saga)-A perfect example of a villian personality. What does an evil conqueror do while his lackeys are off...well, TRYING to conquer? Learn to play the guitar, stack dominos, or wait...perhaps Dating Sim games?
Legato Bluesummers(Trigun)-Need I say more?
Kianu Fallwind (Wild Arms)-At first, he makes a decent obstacle assassin dude, but in his last, confused chaotic moments, he does the one thing which qualifies him as a big time villian: blows his own head off, to make sure Sheyenne can never get his body back. He will be remembered...
Dilandau (Escaflowne)-The most psychotic villian I have even seen in any anime period. His glory cannot be described, you just have to see the anime yourself. You'll either laugh, or cry, because he IS a total psychopath