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Because a level 100 Pokemon can no longer level up, it cannot learn new moves in that way. However, move tutors can teach a Pokemon new moves regardless of level, as can TMs and HMs. In Diamond, Pearl, and Platinum, there is also a man who will teach your Pokemon moves it could have learned at earlier levels in exchange for a Heart Scale.

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Q: Do level 100 daycare Pokemon learn new moves in diamond?
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