PokéBase - Pokémon Q&A
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1 vote

The earliest it can be obtained is upon beating the third gym. On Route 36, after you defeat Whitney, gain the SquirtBottle, and interact with the Sudowoodo blocking the route, you can find Schoolboy Alan near the routes end to the east. If you talk to him, you can get his phone number registered in your Pokegear. When he calls, he'll offer to give you a Fire Stone the next time you see him. When he calls is purely random, so it may take you a while, but that is the earliest available option if you're looking to get a Fire Stone before beating the E4.


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1 vote

Before beating the E4, you can get a Fire Stone on Tuesday at the Pokeathlon Dome for 2500 points, or by being given one by school kid Alan on Route 36, who will sometimes give you one if you have his number registered in your Pokegear.

Source 1, source 2

edited by
The Pokeathalon method only works post-National Dex
On Sunday and Thursday, yes, but Tuesday allows you to buy one pre-natdex.
Ahh, my mistake