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I heard Breloom gets spore at 55 or something? Is this true? Nope, it's Shroomish. You have to keep it unevolved to learn Spore.
Or which would be better than breloom? Spore has 100% Acc, so those that learn it are ideal, namely the Shroomish line and Smeargle. Additionally, Compound Eyes increases Acc, so Butterfree, Venonat and Yanma can help, but don't reach 100% Acc with their respective sleep moves.