Developing　high-efficient　photocatalysts　for　H2　production　is　still　the　focus　of　current　research.　A　series　of　CoSx/Zn0.3Cd0.7S　(CoSx/ZCS)　samples　with　different　mass　ratios　were　successfully　synthesized　for　H2　production　by　the　oxidation　of　p-chlorobenzyl　alcohol　(Cl-PhCH2OH).　Herein,　Zn0.3Cd0.7S　(ZCS)　solid-solution　nanoparticles　are　distributed　on　the　surface　of　CoSx　polyhedron,　and　CoSx　is　obtained　from　ZIF-67,　composed　of　Co1−xS　and　CoS2.　The　photocatalytic　H2　production　was　performed　by　Cl-PhCH2OH　oxidation　in　N,N-Dimethylformamide　(DMF)　solution　under　visible　light　irradiation,　and　5%　CoSx/ZCS　sample　showed　the　best　photocatalytic　activity,　with　the　H2　generated　rate　high　to　2.80 mmol g−1 h−1.　Meanwhile,　the　selectivity　of　Cl-PhCH2OH　oxidation　to　p-chlorobenzaldehyde　(Cl-PhCHO)　is　97.6%,　and　the　rate　is　2.95 mmol g−1 h−1.　Moreover,　the　reasons　for　the　excellent　photocatalytic　performance　of　CoSx/ZCS　samples　were　deeply　analyzed　by　experimental　and　theoretical　results,　such　as　trapping　agents,　photoelectrochemistry　test,　electron　paramagnetic　resonance　(EPR),　specific　surface　area,　and　density　functional　theory　(DFT)　calculation.　This　work　provides　a　new　theoretical　guidance　and　experimental　experience　for　the　application　of　H2　application　and　design　of　novel　photocatalysts.　©　2023　The　American　Ceramic　Society.