PokéBase - Pokémon Q&A
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Professor Juniper gives you one, right after you walk out of the 8th gym.

EDIT: I forgot, you can also get one in the castelia pokemon center, if you have traded with 50 people.

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And if you're wondering, the 8th gym is in opelucid city.
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And a man in castelia city gives you one after you trade 50 times he is in the pokemon centre top floor

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Basically you can get a masterball in two places. One, like J98 said, you get right in front of the gate to route 10. You must beat the 8th gym first. Second, like james said, you can get in the Castelia City pokemon center when you have traded 50 times. Good luck getting them!

Hope this helps =)

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So, you can two masterball? Really?