PokéBase - Pokémon Q&A
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I've tested back in Gen 4 to see what they looked like when you used them (when they opened to encapsualate a Pokemon), and they do look quite marvelous even back then. I cheated for them, of course.

But has there ever been any way, maybe through an item distribution event that I don't know about or otherwise (I doubt), in which you could actually obtain empty Cherish Balls? I don't expect that there is but it's always nice to make sure instead of always rely on an assumption.

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no
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i figured