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The photoreduction of CO2 to chemical fuels represents a promising technology to mitigate the current energy dilemma and global warming problems. Unfortunately, the original photocatalysts suffer from many side reactions and a poor CO2 conversion efficiency. The rational combination of active co-catalyst with pristine photocatalysts for promoting the adsorption and activation of CO2 is of vital importance to tackle this grand challenge. Herein, we rationally designed a SnIn4S8 nanosheet photocatalyst simultaneously equipped with CuAu alloys. The experimental results proved that the CuAu alloy can trap the electrons and enhance the separation and transport efficiency of the photogenerated carrier in the photocatalyst, alleviating the kinetical difficulty of the charge transfer process because of the preferable localized surface plasmon resonance (LSPR). Furthermore, the CuAu alloy works as the synergistic site to increase the CO2 adsorption and activation capacity. The optimized CuAu-SnIn4S8 photocatalyst exhibited a superior performance with CO generation rates of 27.87 μmol g−1 h−1 and CH4 of 7.21 μmol g−1 h−1, which are about 7.6 and 2.5 folds compared with SnIn4S8. This work highlights the critical role of alloy cocatalysts in boosting a CO2 activation and an efficient CO2 reduction, thus contributing to the development of more outstanding photocatalytic systems.