Photocatalytic H 2 evolution and biomass-derived alcohol oxidation is a cooperative way for improving the utilization of photogenerated charge carriers. Herein, a highly efficient photocatalyst was fabricated by decorating Zn 0.5 Cd 0.5 S with a C,N codoped CoP polyhedron (referred to as CoP, derived from ZIF-67), and then it was used for H 2 evolution and 5hydroxymethylfurfural (HMF) oxidation. For the optimized sample (20% CoP/Zn 0.5 Cd 0.5 S), the generated H 2 rate is significantly enhanced from that of the HMF aqueous solution with 2,5-diformylfuran (DFF) as a concomitant product, about 31.7 times higher than the pristine Zn 0.5 Cd 0.5 S under visible light irradiation. The separation of photoexcited electrons (e − ) and holes (h + ) in the process was promoted, as both e − and h + were involved in the desired conversions. From the results of density functional theory (DFT) calculations and in situ XPS spectra, the utilization of e − was further improved as a spontaneous transfer from Zn 0.5 Cd 0.5 S to CoP occurred due to the p−n heterojunction formed between Zn 0.5 Cd 0.5 S (n type) and CoP (p type). This work provides an efficient method to separate the photoinduced charge carriers and a new way for H 2 evolution accompanied by transformation of HMF to DFF.