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Heterojunctions coupled into micro‐mesoscopic structures is an attractive strategy to optimize the light harvesting and carrier separation of semiconductor photocatalysts. A self‐templating method of ion exchange is reported to synthesize an exquisite hollow cage‐structured Ag2S@CdS/ZnS that direct Z‐scheme heterojunction photocatalyst. On the ultrathin shell of the cage, Ag2S, CdS, and ZnS with Zn‐vacancies...