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Ultrafine CuS nanoparticles anchored on nitrogen-sulfur co-doped graphene nanosheets are synthesized by a simple-green solvothermal method, the composite has excellent electrochemical performance for CO 2 reduction. [Display omitted] • The CuS/N, S-rGO was synthesized via a facile and environmentally friendly method. • The co-doping of N and S on graphene can promote the activation and conversion of CO 2. • CuS/N, S-rGO exhibits outstanding formate selectivity for CO 2 RR. Electrochemical conversion of CO 2 into hydrocarbons can effectively alleviate the energy crisis and promote carbon cycle. Herein, we report that small-size CuS nanoparticles are confined in nitrogen and sulfur co-doped reduced graphene oxide (CuS/N,S-rGO) for electrochemically reducing CO 2 to formate. Specifically, the CuS/N,S-rGO electrode achieves maximum Faradaic efficiency of 82% for formate formation at −0.63 V versus the reversible hydrogen electrode (RHE). Moreover, this catalyst exhibits a stable performance during 20 h-electrolysis. Experiments demonstrate that the doping of nitrogen and sulfur can create an abundance of active sites on the graphene nanosheets to accelerate the CO 2 reduction reaction (CO 2 RR). The CuS/N,S-rGO electrode exhibits excellent performance for CO 2 RR is attributed to the synergistic effect between N,S-rGO and CuS, and graphene can improve stability of composite. This work provides an efficient electrocatalyst for CO 2 RR and offers a facile and environmental friendly approach to synthesize small-size Cu-based composites. [ABSTRACT FROM AUTHOR]