At level 12 From This Question you start to obtain great balls when leveling.
I am currently level 6 and have only ever gotten normal pokeballs from pokestops.
Is there at any point (possibly after 12) where pokestops start giving better balls?
Pokemon-go – Great Ball at PokeStops
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Best Answer
I am level 12 and once you "unlock" the great ball it will be dropped at pokestops. They are harder to get than normal pokeballs. This goes for nearly every item (eg. razzberries, super potions, etc).