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I know there's a TM for Sunny Day, however I want to know which obtainable Pokémon can learn it naturally, either in its starting moveset or through level up. I know Rapidash starts with it, but are there any others?

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It looks like Magmar and Seedot are the only Pokemon in that game that learn it naturally. Seedot gets it at 31 and Magmar gets it at level 33. Seedot's evolutions though don't seem to learn it in this generation, so you have to stop it from evolving and I think the Magmar you get in this game is higher than that level and doesnt have it when you snag it, so you would need to use the move relearner.

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How do you know this?
https://m.bulbapedia.bulbagarden.net/wiki/Sunny_Day_(move)

https://www.serebii.net/xd/pokemon.shtml

The second link shows all the snagable pokemon in XD (it doesn't seem like any of the other obtainable pokemon can learn it from things like the PokeSpot) and the first link has a list of all pokemon that learn sunny day by level up. Those two are the only ones that can learn it via level up in gen3.
Off of your sources, Seedot seems to learn Sunny Day at level 31 instead of at level 33, and off of what I know, Magmar may or may not have the move Sunny Day when caught, as its caught at level 36.
My mistake I'll change that