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Think by completing piccolos missions.
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I did all the ones he would give me I'm a 26 do I have to be a higher lvl to unlock more of his or what bc I did what he asked an now he doesn't say anything about learning another one after I did his 2nd mission
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Ya I think all the mentors have 5 or so that you have to do in order to learn their master move. You have to level up or get a certain amount of something b/c sometimes my mentor has shit for me to do right before I'm about to level.