PokéBase - Pokémon Q&A
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My Ampharos unlocked it once. I'm not sure how it did it, but after it used it a few times, I put it in the PC and tried to get another Pokemon to use it. But it wasn't there! My Ampharos couldn't even use it after that! What?How?Help?

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You unlock after you complete level 1, 2, and 3 all the different stats, for each Pokemon they have their own progression. You should still be able to access it with Ampharos though.

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You unlock secret super training when the Pokemon has maxed evs. Pokemon that still need evs can't not participate in secret super training.

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To add a bit more [useless] information on Super Training...

Actually, it will unlock if ALL Pokemon in your party are fully EV trained. It still works if all Pokemon's EV's have been Reset to 0. How? Past Experience, as I have apparently cleared around 2,000 ST Regiments. (lol). To Know that a Pokemon is fully EV trained, It'll say it's stats cannot go higher, and it will show some symbol in the upper left corner. A Pokemon that has successfully completed/cleared all Super Secret Training Regiments will have the original fully EV trained symbol, along with five stars in the bottom. The Super Secret Training Record of that Pokemon will reset if you trade it to another person.

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