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Humans CAN be caught in pokéballs. If they can capture and contain the creator of the universe, it only makes sense that regular-ass humans can be caught as well. However, I do believe there are rules that shatter some of the fantasies some have with this concept.
For starters, humans aren't trapped inside. Much like how we've seen pokémon exit their balls when they want, so too would humans. I'm not sure exactly HOW they can leave. But rest assured they can.
Secondly, they wouldn't be forced to obey the person who caught them. Perhaps the balls have some pacifying on pokémon but I think humans have higher brain function and wouldn't be affected.
Lastly, I believe there are machines similar to metal detectors in most buildings that keep tabs on a trainer's pokemon. So it's not like you could use it smuggle people or some shit. I imagine you could be arrested if you're caught with a human in a pokéball.
So what would be the benefits of a human capturing another? I can only think they're would be some sort of sexual aspect to it, similar to pet play you know? "Poké Play" if you will.