Photocatalytic hydrogen production coupled with high value-added organic conversion is a mild and effective way to obtain green energy and fine chemicals simultaneously. In this work, a CdS-based S-scheme photocatalyst is designed for efficient hydrogen production and highly selective conversion of benzyl alcohol in aqueous solution. With further assistant of Ni co-catalyst, the hydrogen production rate of WOx/CdS S-scheme photocatalyst can reach ∼131 μmol h−1, and benzyl alcohol has ∼91% conversion with selectivity of the target product benzaldehyde ∼100 %. The quality photocatalytic activity is inclined towards the construction of S-scheme heterojunction composing of WOx and CdS can ensure the redox ability while reducing the recombination of photogenerated carries. Meanwhile, reactive species involved in benzyl alcohol oxidation were confirmed by radical capture experiments, the excellent conversion and selectivity could not be achieved without the significant contribution of photogenerated holes.