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Designing S-scheme heterojunctions is an effective method to improve the charge localization on the surface of photocatalysts. Their effective charge transport routes can be enhanced with the help of interfacial noble metal nanoparticles. Herein, an Ag/CuO@ZnIn 2 S 4 plasma S-scheme heterojunction with heterogeneous interfacial covalent bonds was successfully designed. The 15% Ag/CuO@ZnIn 2 S 4 has promising photocatalytic performance and stability with the highest CO and CH 4 yields of 6.9 and 54.4 µmol g−1 h−1 and CH 4 selectivity of 92.8%. It is evidenced that the photogenerated charge can be efficiently separated and transported due to the influence of both the S-scheme electron migration mode and the Cu-S covalent bond. The process is further accelerated by using precious metals as cocatalysts, which can then selectively convert CO 2 into CH 4. This research is expected to provide helpful information for engineering S-scheme heterojunction photocatalysts and investigating their charge transfer kinetics. [Display omitted] • Design of a S-scheme heterojunction to promote the separation of carriers. • Built the Cu-S bonds to accelerate the transfer of charges. • Utilizing the LSPR effect to generate hot electrons and enhance light absorption. • The Ag/CuO@ZnIn 2 S 4 photocatalysts can selectively reduce CO 2 to CH 4. [ABSTRACT FROM AUTHOR]