Hiding behind the bushes there is a Mankey watching the gang as they eat their food. Hoping to get some of it, the pig-monkey approaches Brock playfully, so he gives it a rice ball. For Ash, this is an unexpected chance to catch a fighting Pokémon.
Acting before thinking, and ignoring Misty's advice, Ash throws a Poké Ball at Mankey without weakening it first, to which the pig-monkey reacts by throwing the rice ball back, frustrating the poorly executed catch attempt.

Is that a Mankey behind the bushes?

Season 1 - Episode 25
"Primeape Goes Bananas"
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