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Was the Masterball ever used in the anime?

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Does anyone ever use this in the anime except for the videogames?

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Yes. There were two cases, one not so much though...

  • Misty threw a Masterball beach ball at Ash in episodes Beauty and the Beach and A Hot Water Battle.
  • A real Masterball appeared in the episode Whiscash and Ash, where a fisherman attempts to catch an oversized Whiscash, but the Whihscash swallowed the Masterball.

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lol whiscash
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FAY-YUL!