what does "call it off" mean?
in one episode of Friends, Frank said "she called it off" saying her girlfriend wanted to break up. Does it mean breaking up or it could mean something else?

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It basically means "to cancel". To call something off is to cancel something.

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I think a better definition would be "to break on a promise." It happens when you change your mind about an arrangement, be it physical, emotional, or otherwise.

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Kevin is correct about Allen's answer.  It means to cancel something which most often is about to occur or has not come to a conclusion.  Call off: a party, a wedding, a engagement, etc.

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You should have picked Andrew's answer as it is the only correct one