PokéBase - Pokémon Q&A
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Now let's say some maniac went and filled up his PC before going to Professor Scyamore to fight him and get one of the Gen 1 starters. What would happen? Who the heck cares?! I do!
Now I'm not sure if you could get enough money to buy enough Pokeballs, I vaguely remember there's a way to get infinite money using Premier Balls by selling the Pokeballs you bought, not 100% sure (not even sure that's how you do it). I think that was a gen 7 exploit or maybe not?
( Can some mad lad like hack or something and test this out )

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I'm willing to do this but it might take some time
noice
(filler)
I think it will say your pc is full and wait. Good question tho

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This YouTube video shows that if you fill all 30 of your Boxes and attempt to catch an optional Pokemon, it will display a message saying your PC Boxes are full.

If you catch Xerneas/Yveltal (which are required to complete the game) with full Boxes, a new Box 31 will appear. This Box is only unlockable if you've filled your other 30 and are required to catch a Pokemon to proceed with the story. Because you need to accept a Kanto starter from Professor Sycamore to proceed, it's safe to assume that Box 31 will also appear if you have no room for a Kanto starter.

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Proffesor Sycamore says this if party is full :
"Oh! So you don't want it right now? Come back and get your Pokémon once you've organized your PC Boxes."
I think it would be the same for PC being full.

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Source?