Photocatalytic hydrogen evolution coupled with benzyl alcohol oxidation to val-ue-added chemicals offer an efficient route enabled by CdS. However, the charge recombination and photocorrosion of CdS towards the low productivity of H2 and benzalde-hyde. Herein, a novel fluorenone-based covalent organic framework (COF) is coupling with a CdS S-scheme heterojunction. The suitable band level and active center of fluorenone moiety endows the fluorenone-based COFs with strong oxidative capability towards benzyl alcohol and a low reaction energy barrier. Furthermore, the built-in electric field created by the constructed S-scheme heterojunction effectively enhances the separation and migration of photogenerated charge carriers while suppressing carrier recombination within each sem-iconductor, thereby reducing the corrosive effect of photogenerated holes on CdS. Conse-quently, the heterojunction significantly improved the productivity of benzaldehyde and hy-drogen production activity. In the presence of Pt as a co-catalyst, the production rates of H2 and benzaldehyde reached 23.38 and 17.36 mmol g-1 h-1, respectively. This work not only addresses the challenges associated with the utilization of electron holes but also paves an effective green and low-carbon pathway to overcome the issues of low efficiency and high costs in photocatalytic hydrogen production.