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This invention relates to the field of composite coating technology, specifically to a composite coating for an aluminum-silicon wire submerged roll, its preparation method, and its application. The method involves sequentially depositing CoCrW, CoCrW-Ca2SiO4, Ca2SiO4, and Si-SiC, or sequentially depositing Ca2SiO4 and Si-SiC, on the surface of the submerged roll using atmospheric plasma spraying (APS). Subsequent machining then yields a four-layer CoCrW / CoCrW-Ca2SiO4 / Ca2SiO4 / Si-SiC composite coating or a two-layer Ca2SiO4 / Si-SiC composite coating (hereinafter referred to as the composite coating) with a specified surface roughness. The composite coating prepared by the method described in this invention can withstand temperatures up to 900℃ and possesses excellent wear resistance and aluminum-silicon corrosion resistance, significantly improving the lifespan of the submerged roll.