He got the form during the 7 years between the Cell Games and Buu saga. First time shown was majin vegeta vs. goku. First time its used clean (without majin or any other influences) vs. kid buu
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Vegeta does not go super saiyan 2 when he goes majin like some people say. He actually goes super saiyan 2 sometime during the 7 years Goku is in other world after being blown up by Cell. It is unclear when in that time period, but when he is training with kid Trunks, and Trunks goes super saiyan, Vegeta is a super saiyan 2 then. You can tell because his muscles are bigger than regular super saiyan but not as big as Super Vegeta's muscles. His hair is also longer.
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He goes super saiyan 2 during the cell saga after Goku dies and he gets mad and cell and his anger was enough to make him transform into SSJ2 but was very cocky in his SSJ2 form.
214 vegeta,s pride
In the Majin Buu Saga after Buu was resurrected. When Vegeta was in the heavens after he died, he saw Goku go SS3 and accused Goku of mocking him with that transformation. In case you were looking for the episode number it was episode 245
Here they are:Goku: Super Saiyan 1, 2, 3, and 4Vegeta: Super Saiyan 1, Ultra Super Saiyan(Ussj), Super Saiyan 2, and 4.Trunks: Super Saiyan 1, Ultra Super Saiyan(Ussj), and Super Saiyan 2.Gohan: Super Saiyan 1, and 2.(Though he has Ultimate Gohan form, it doesn't really count.Teen Gohan: Super Saiyan 1, and 2.Kid Gohan: He doesn't turn Super Saiyan yet.Goten: Super Saiyan 1.Broly: Legendary Super Saiyan.(The rest like 1, 2, or 3 are not shown in DBZ)Gogeta: Super Saiyan 1, and 4.Vegito: Super Vegito(Which I think counts.)
For literary reasons, at the end of Dragon Ball Z Goku regained the spot of being on top as the series ended, with Vegeta finally excepting that Goku is stronger then him. Bringing closer to the series.
you beat the legendary super saiyan saga .