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By earliest, I mean earliest in the game, and by when I mean is there any good moves Vulpix learns that I should wait for?

There's a stone store in Lumiose, and I believe you have access to it the first time you visit, which is pretty early on in the game, if I'm not mistaken.

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The earliest you can find a Fire Stone is on Route 9. And I would suggest evolving Vulpix into the glorious Ninetales at Lv. 34, when it learns Flamethrower, or Lv. 39 if you want it to know Extrasensory.

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Thank you, very helpful
It already knows Extrasensory from an egg move, this is a very good Vulpix.
you can get a fire stone on route one with super training