Lead halide perovskite (PVK) has been deemed as a promising photocatalyst alternative because of its remarkable photoelectrical properties; however, the severe charge recombination has limited its catalytic activity. Herein, we report a PVK-based Z-scheme heterojunction, a-Fe 2 O 3 /Amine-RGO/CsPbBr 3 , for highefficiency CO 2 reduction in the presence of H 2 O. By delicately controlling the interfacial interaction, effective Z-scheme electron transfer from a-Fe 2 O 3 to CsPbBr 3 is built, leading to boosted charge separation and prolonged carrier lifetime, as confirmed by electron spin resonance (ESR), transient absorption (TA) spectra, etc. The impactful spatial separation of photo-generated carriers in Z-scheme system finally enables an 8.3-fold enhancement in photocatalytic performance as compared to CsPbBr 3 . A stable product yield of 469.16 mmol g À1 and an electron consumption yield of 3,132.46 mmol g À1 are achieved. This work is expected to provide deep insights into boosting the photocatalytic performance of PVK by modulating the charge carrier dynamics.