Photocatalytic conversion of solar energy into hydrogen and high value-added fine chemicals has at- tracted increasing attention. Herein, we demonstrate an efficient photocatalytic system for simultane- ous hydrogen evolution and benzaldehyde production by dehydrogenation of benzyl alcohol over Ni- decorated Zn 0.5 Cd 0.5 S solid solution under visible light. The photocatalytic system shows an excellent hydrogen production rate of 666.3 μmol h ? 1 with high stability. The optimal apparent quantum yield of 52.5％ is obtained at 420 nm. This noble-metal-free photocatalytic system displays much higher activity than pure Zn 0.5 Cd 0.5 S and Pt-loaded Zn 0.5 Cd 0.5 S solid solution. Further studies reveal that the metallic Ni nanocrystals play an important role in accelerating the separation of photogenerated charge carriers and the subsequent cleavage of α -C-H bond during dehydrogenation of benzyl alcohol.