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I know there are moves like Roost, Rest, and Recover, with 10 PP, and moves like Synthesis, with only 5 PP. Is there a healing move with more PP?

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Purify, Aqua Ring, Pain Split and Ingrain hold that distinction, capping out at a maximum of 32 (Base 20 PP).

As for direct healing of 50%, Milk Drink, Recover and Roost are next with a maximum of 16, base 10.

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Don't all 50% recovery moves have 10 PP except synthesis, morning sun, and moonlight?
Maybe.