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The ability to create perovskite-based heterostructures with desirable charge transfer characteristics represents an important endeavor to render a set of perovskite materials and devices with tunable optoelectronic properties. However, due to similar material selection and band alignment in type-II and Z-scheme heterostructures, it remains challenging to obtain perovskite-based heterostructures with a favorable electron transfer pathway for photocatalysis. Herein, we report a robust tailoring of effective charge transfer pathway in perovskite-based heterostructures via a type-II to Z-scheme transformation for highly efficient and selective photocatalytic CO₂ reduction. Specifically, CsPbBr₃/TiO₂ and CsPbBr₃/Au/TiO₂ heterostructures are synthesized and then investigated by ultrafast spectroscopy. Moreover, taking CsPbBr₃/TiO₂ and CsPbBr₃/Au/TiO₂ as examples, operando experiments and theoretical calculations …