In this paper, Cu-doped MoS2 (Cu-MoS2) acting as an efficient co-catalyst was successfully attached to the surface of Cd0.6Zn0.4S via the solvothermal method to formed a unique Schottky structure. Cu-MoS2/Cd0.6Zn0.4S (6499.66 μmol/g/h) showed a greatly enhanced photocatalytic hydrogen production yield that was 73.47 times higher than those of pure CdS (88.47 μmol/g/h). Better light absorption, a remarkable photo-generated charge separation and transfer capacity, and greater availability of HER active sites were observed in Cu-MoS2/Cd0.6Zn0.4S. In all, combining with efficient co-catalyst is a promising method for providing photocatalytic hydrogen evolution reaction (HER) sites and promoting interfacial charge separation and transfer for improved photocatalytic hydrogen production.