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you can do challenge missions[for legendaries] when you get the master three star rank.If you don't want to do it for legendaries you don't need to have the master three star rank.

Obtain these challenge requests at spindas cafe or use wonder mail codes or wondermail generator.

If you want the seven treasures rescue scizor in crevice cave.

[mr mime will appear beside kecleonsshop talk to him and he will give u the mission]

get this after beatingthe chapter game

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Q: When can you do challenge request missions in Pokemon mystery dungeon explorers of the sky?
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