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.