(I'm just gonna list them favourite to least favourite and only ones I've actually seen.)
Batman: Kevin Conroy
, Michael Keaton, Val Kilmer, Adam West, Ben Affleck, Christian Bale, George Clooney
Joker: Mark Hamill
, Cesar Romero, Troy Baker, Jack Nicholson, Heath Ledger, Jared Leto
Superman: Christopher Reeve
, George Reeves, Tom Welling, Kirk Alyn, Dean Cain, Brandon Routh, Henry Cavill, Gerard Christopher, John Haymes Newton, Tyler Hoechlin
I'm going to have to come back to this thread though, there are some characters like Dracula who have so many portrayals I'm going to have to actually figure out who comes after Christopher Lee and in what order.