PokéBase - Pokémon Q&A
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I have a sick moveset idea for doubles and it requires Switcheroo, but if I could get Headbutt on Ambipom it would be even better because of the STAB flinch-rate. Unfortunately, Switcheroo isn't an EM in Gen 4 where Ambipom can learn Headbutt via Move Tutor... Is it in anyway possible to get both moves without hacking?
I don't think so, but I'll ask anyway out of desperation :P

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What is an EM?

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It is not possible to have them both.

source: this site's move pages and smogon

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Yeah I figured, but I always ask anyway. Thanks.