Photooxidation of biomass alcohols coupling H2 evolution has received increasing attention due to its higher economy. However, the insufficient photoexciton utilization has become a bottleneck restricting its practical application, thereby precisely regulating the microstructure of photocatalysts is crucial for achieving efficient photoactivity. Strategically introducing functional active centers has been proven to be a valid strategy for optimizing the exciton dynamics of photocatalysts. Herein, the cobalt (Co) clusters and single-atom Co-O sites were co-decorated on the heterostructured MoS2/CdS composite to integrate the merits of heterojunction and non-precious metal cocatalysis, which was demonstrated by the X-ray absorption fine structure spectroscopy and spherical aberration-corrected transmission electron microscope techniques. Remarkable collaborative photoactivity for benzyl alcohol oxidation (181.8 mmolBAD·g-1·h-1) coupling H2 evolution (64.6 mmolH2·g-1·h-1) was achieved under artificial sunlight. Femtosecond transient absorption spectroscopy and Kelvin probe force microscopy techniques proved the improved spatial separation/transfer kinetics and hindered recombination kinetics of photoexcitons. Based on density functional theory, the Co clusters act as the oxidation sites for benzyl alcohol, and the Co-O sites serve as the H2 evolution reduction centers, enabling the synergistically enhanced REDOX half-reactions due to more effective spatial separation of photoexcitons. This study proposes a strategic catalyst construction insight for high-efficient collaborative REDOX photocatalysis.