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There are quite a few moves that can make your opponent fall asleep:

Hypnosis - 60% Accuracy - Psychic

Dark Void - 80% Accuracy - Dark

Grasswhistle - 55% Accuracy - Grass

Lovely Kiss - 75% Accuracy - Normal

Sing - 55% Accuracy - Normal

Sleep Powder - 75% Accuracy - Grass

Spore - 100% Accuracy - Grass

Yawn - '--' Accuracy - Normal - (At the end of the turn after using Yawn, the target falls Asleep unless it is switched out.)

Courtesy of Pokemon.Marriland.com

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If you're doing the Pokemon Leaf puzzle on Pokemon.com, then the answer would be spore.

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Q: A Pokemon move that makes the opponent fall asleep?
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