Herein, interfacial and defect-engineering strategies synergistically promote photocatalytic properties. Because of the matching energy levels and the close interfacial contact, the CeO 2 @ Cu-TCPP S-scheme architecture is successfully constructed via the in situ wet chemistry route. Photothermal conversion assists abundant O Vs on the CeO 2 compartment. Strong evidence of an S-scheme charge transfer path is verified by density functional theory (DFT) calculations and in situ irradiated X-ray photoelectron spectroscopy (XPS). This S-scheme heterojunction system is more deep-seated in facilitating the separation and transfer of photogenerated carriers as well as acquiring strong photoredox ability. Meanwhile, the abundant O Vs proved by XPS and electron paramagnetic resonance spectra (ESR) enhanced the light-harvesting capacity and conductivity and shortened the transfer route. As a result, this synergistic heterojunction could mostly promote photocatalytic CO 2 activation. The typical 0.25CeO 2 @ Cu-NS exhibited the best photocatalytic CO 2 RR to form CO and CH 4 (rate: 229.6 μmol•g −1 ), which is even 45.8-and 1.5-folds higher than those of pristine LA-CeO 2 (5.0 μmol•g −1 ) and Cu-TCPP (152.2 μmol•g −1 ), respectively, higher than those of other reported CeO 2 -based photocatalysts. This study presents a reinforcement and matrix prospect for domain charge behaviors to accelerate CO 2 activation.

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