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This invention relates to the field of photocatalytic materials technology, specifically to a polybenzoxazine aerogel microsphere photocatalyst, its preparation method, and its application. The invention uses γ-aminopropylmethyldiethoxysilane, phenol, and paraformaldehyde as raw materials to synthesize benzoxazine with Si-O-C bonds and a planar π-conjugated structure. Then, the benzoxazine monomer undergoes ring-opening polymerization, followed by an in-situ emulsion template gelation method to form a polybenzoxazine aerogel microsphere catalyst with a wrinkled surface structure. The planar π-conjugated system and the interaction of tertiary amine groups in the polybenzoxazine aerogel microsphere catalyst promote the adsorption and activation of O2, as well as the gradual proton and electron transfer, thereby achieving highly efficient H2O2 photocatalytic synthesis. The preparation method of the polybenzoxazine aerogel microsphere catalyst of this invention is simple, the raw materials are readily available, and the cost is low.