| Villain | Actor |
| Riddler (seasons 1 & 3) | |
| Riddler (season 2) | |
| Penguin | |
| Joker | |
| Mr. Freeze (season 1) | |
| Mr. Freeze (season 2) | |
| Mr. Freeze (season 2) | |
| Zelda / Olga, Queen of the Cossacks | |
| Mad Hatter | |
| False Face | |
| Catwoman (season 1 & 2) | |
| Catwoman (season 3) | |
| Catwoman (1966 movie) | |
| King Tut | |
| Bookworm | |
| The Archer | |
| The Minstrell | |
| Ma Parker | |
| | Villain | Actor |
| Clock King | |
| Egg Head | |
| Shame | |
| Sandman | |
| Chandell | |
| The Puzzler | |
| Marsha, Queen of Diamonds | |
| Colonel Gumm | |
| Black Widow | |
| Siren | |
| Louie the Lilac | |
| Lola Lasagne | |
| Lord Ffogg | |
| Lady Pea Soup | |
| Nora Clavicle aka Police Woman | |
| Dr. Cassandra | |
| Minerva | |
|