The Joker (Cesar Romero) possesses a twisted, malevolent sense of humor. The Joker has a habit of overpowering the station in charge of the news, and gives the Dynamic Duo clues to his crimes.
The Penguin (Burgess Meredith) baffles the Caped Crusaders with his bird and umbrella clues as to what crime he is going to commit.
The Riddler (Frank Gorshin, also played once by John Astin) has a compulsion to present riddles that give Batman clues to his crimes. The Riddler's mind works in a twisted way. As Batman said in the first episode, "The Riddler's mind is like an artichoke. You have to rip off spiny leaves to reach the heart!"
Catwoman (Julie Newmar in the first two seasons, then Eartha Kitt, Lee Meriwether in Batman: The Movie): Her crime sprees emphasize a cat motif. Catwoman secretly loves Batman, but she still likes to try to murder him and Robin. In the third season Catwoman displayed no underlying affection for Batman, but harbored particular antipathy toward Batgirl (Yvonne Craig).
Mr. Freeze (played once each by George Sanders, Otto Preminger, and Eli Wallach) facilitates his crimes by freezing people and objects with a blast of his deadly "freeze gun" (which is also a flame-thrower on some occasions). Mr. Freeze is forced to live in an environment 50 degrees below zero.
The Mad Hatter (David Wayne): An inventor who uses his many hats to hypnotize people.
Egghead (Vincent Price): the self-proclaimed "world's smartest criminal".
King Tut (Victor Buono): an obese Yale Egyptologist who, after a blow to the head, believes he is a real pharaoh, with a gang of hoods who also believe the delusion.
Joan Collins as The Siren, Roddy McDowall as The Bookworm, Walter Slezak as The Clock King, and Art Carney as The Archer. Tallulah Bankhead's role as the Black Widow turned out to be her final screen appearance. (from Wiki)