The simultaneous efficient utilization of photon-generated carriers to realize the selectively photocatalytic oxidation of organics coupled with hydrogen evolution has gained ever-increasing attention in the energy sector. A series of CdS/P25/Ni₂P (S_xO_yP) was prepared, in which, S₁O₁P showed the highest activity. The conversion, selectivity, and yield are 97.47, 100, and 97.47%, respectively. Moreover, in consideration of the practical application of photocatalysis, the substrate concentration was expanded to 300 mM, which significantly exceeded that of the usually reported benchmark for photocatalysis, and the rate of hydrogen evolution could reach up to 16 697.86 μmol g_cat⁻¹ h⁻¹ under light irradiation for 3 h. Based on the experimental data and analysis, a possible mechanism for this reaction was proposed. This paper provides a strategy for making full use of photocarriers and explores the field of dual-function photocatalytic systems, which will be inspirational for the development of photocatalysis technology.