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Can some Mega stones only be obtained after beating the E4?

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Can some Mega stones only be obtained after beating the E4?

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Yes. Absolite, Medichamite, Gardevoirite, Houndoomite, Manectite, Tyranitarite, and Mewtwite are found after the Elite Four.

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*Mewtwonite
you forgot Aggronite.

And some Mega Stones are exclusive to either X or Y.
Mawilite, Gengarite, Gyradosite, Banetteite, Scizorite, and the Mega stones for the two starters you didn't pick.