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According to Serebii, Charizard is one of the Rare Spawns, but I was wondering whether it, like Dragonite, spawned in the sky, which is only accessible post elite four, or if it would appear alongside Pokemon like Squirtle.

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Charmander can be found pre-E4 on several routes, so yes.

Source: https://pokemondb.net/pokedex/charmander
I mean charizard itself, without having to evolve it
Ah, I see. Charizard's page on this site says no, but LGPE are newly released and the site's missing a lot of locations.
According to a random Smogon post, no, but it might be excluding evolved Pokemon.  https://www.smogon.com/forums/threads/wip-lets-go-in-game-tierlist.3644062/

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Here are the locations of where you can find a Charizard in LGPE:

Route 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 25

Please note that you can definitely find a Charmander on Route 3/4/24 (Gift after catching 50 total Pokemon), and in Rock Tunnel.

EDIT: You can find Charizard high in the sky like Dragonite, so you can only find your Charizard in the post-game OR on Route 17 "Pokémon Road".

MunchingOrange mentions at Timestamp 7:44 of his most recent video that this Route is the only one pre-post-game that you can fly high.

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Are you sure Charizard can be found on those routes before the player beats the champion?
Those are just the places you can find it. If you want a Charizard b4 the E4, I'd say evolve your Charmander.

Pokemon who fly high like the "Zard" can most likely be found later on after E4.