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I'm wondering since I've been in the post game and I'm pretty sure I've been in Ancient Poni Path, but Dexio hasn't shown up.

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This has nothing to do with how you get the key stone/mega evolution availability in-general.

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How to unlock Mega Evolution in S/M

STEP 1: Head to Ancient Poni Path on Poni Island.
STEP 2: Battle all the trainers there and head to the Battle Tree
STEP 3: At a certain point, you'll be confronted by two characters — Dexio and Sibb — who will challenge you to battle. Once you defeat them, Dexio will give you a Mega Ring and a free Mega Stone for Alakazam, and ta - da, you have unlocked Mega Evolution.

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As for the Mega Stones, refer this answer.

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Ah, so I have to beat all the trainers there, and go towards the battle tree? That's why I haven't seen them, must not have beaten everyone. Thanks!
No, you don't have to have beaten all of the trainers there, you just have to have beaten the Champion, and then on the path to the Battle Tree those guys will stop you.
Okay, I must have missed it/forgotten about it, because I've been to the Battle Tree.
"Battle your way through the gauntlet of powerful trainers on the way to the Battle Tree. At a certain point, you'll be confronted by two characters — Dexio and Sibb" taken from GeniusGatiks source, I think he misinterpreted the "Battle your way through the gauntlet of powerful trainers" as needing to fight all the trainers in the region