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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.
You can get aggronite as soon as you get rock smash just go to rusturf cave and go down the path to where you need rock smash to get through