PokéBase - Pokémon Q&A
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The new Poke Dollars limit is 9,999,999 for XY.

The GameCube, Generation V and Generation VI games allow players to carry up to PokémonDollar.png9,999,999.

Source-I've been overusing the Prize Money O-Power...

            [Bulbapedia Pokemon Dollar Page][1]
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Is it possible to collect a million dollars before taking down team flare? Multiple times are you offered the job for 1,000,000 pokedollars
It'll just be slow to do it without Le Wow being available (only unlocks after Elite 4...) but you'll have to grind that 2-star restaurant. Alternatively you can try cloning big nuggets.

But I personally don't think you will be allowed to join a villain team despite the offer...
I've tried, you won't b allowed to join, I powersaved to get the money