PokéBase - Pokémon Q&A
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My friend mentioned something like this happened in the manga, so I wondered if the same occurred in anime. Such as in battle where the Pokemon exceeded the four move limit.

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I believe that the only two Pokémon to know more than four moves were Ash's Snorlax and Pikachu. Pikachu, at one point, knew Volt Tackle, Quick Attack, Thunder, Thunderbolt, and Iron Tail. As for Snorlax, I am not sure what his five moves were, but if memory serves he knew more than four moves during the Orange Islands Pokémon League.

As the anime progressed, however, Pokémon have strictly adhered to the four-attack rule.

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sceptile with leaf blade, bullet seed, solar beam, slam, quick attack. lots of pokemon broke the limit up till black and white. than the show turned from cool anime based off of game for 6-12, to how to play the game for 2 year olds whose granny's gave both copies of the games for Christmas, even getting rid of VOLT TACKE to keep pikachu at 4 moves.

in the words of Obi-wen Kenobi "oh how the mighty have fallen"
No, Pikachu didn't have Thunder at the time of those moves.
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The alakazam in the episode Power Play uses 7 attacks continuously.

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In the Orange Islands Adventures the Orange League Champion Drake had a Dragonite.
That Dragonite had used Dragon rage,Ice Beam,Water Gun,Thunderbolt,Body Slam and
Hyper beam against Ash's Pokemon in the Orange League Championship battle.

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And Slam, and Thunder, and Fly