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Is it decided just before encounter or all the way when starting a new game? I am thinking of using some in my PWT team

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Just before the encounter. The nature will change if you Soft Reset your game.

Source: Experience

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****. Then it might have been better to wait for this question to be answered before catching them all in my 160 hour game file. A modest Terrakion doesn't seem to be the best.
Ehh no it doesn't XD