not sure if you got the answer from the deleted posts but in case you don't know. Theres 3 storylines; riddler, penguin, and joker. You play as the heroes (batman and robin). Once you beat a storyline, a villain storyline becomes available. When you're playing a mission for the first time, you dont get to pick your character. Catwoman is in the penguin storyline. I believe there's 2 missions with catwoman as a playable character. But once you beat a level, you can replay it as freeplay with any character you have unlocked.
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