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Without cheating.

Pokeballs are availble first. The further you advance in the game the better the pokeballs get. (If you buy 10 pokeballs at once you get a Premier Ball. It is just for show.)

You can get 3 free pokeballs of any kind (EXCEPT masterballs) from the dude next to the pokecentre in Solceon Town if you show him the pokeman he wants to see.

Other wise all pokeballs are available over the counter in the Eliete Four.

serebii.com is really helpful site. Tells you everything. Evolutions, pokeballs, poketech apps. Just Google serebii Pokemon pokeballs or whatever you need.

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Q: How do you get all the pokerballs on Pokemon Diamond?
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