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540 - Adopt a pet Raticate and take it for a swim in Lake Valor only to have it unfortunately drown because rats can't swim and so take it to the PokéCenter to be revived and Nurse Joy be all like "oh hellllll nawwww" so you gotta get all up in her grill like "you wot mate???" causing a huge fight to brake out involving the two biggest crime syndicates in the region, resolved only by you agreeing to leave the PokéCenter with your dripping wet Raticate corpse in your arms as per Nurse Joy's request. :D
541: Tease in all new trainers who bring in a weak Pokémon to be healed, like this
Trainer: Nurse Joy, can you please heal my Magikarp?
You: Magikarp? Ha! Magikarp is for losers!
I can confirm all of these actions would get you kicked out of the Pokemon Center!
But if you want to be technical: 542: Have your Pokemon use Hi-Jump Kick on yourself, tossing you into the air and right out the door without any further action.
548: Bring in a big screen and play a movie with LOTS of Rule 34. Go to next center. Repeat until you are no longer allowed to go into Pokemon centers.
555. Give yourself a haircut without using HM Cut, and then when Officer Jenny arrives to interrogate you, make sure to say: "Oh, officer! I can explain!"