Semiconductor photocatalysis is an effective strategy for solving the problems of increasing energy demand and environmental pollution. ZnIn2S4-based semiconductor photocatalyst materials have attracted much attention in the field of photocatalysis due to their suitable energy band structure, stable chemical properties, and good visible light responsiveness. In this study, ZnIn2S4catalysts were modified by metal ion doping, the construction of heterojunctions, and co-catalyst loading to successfully prepare composite photocatalysts. The Co-ZnIn2S4catalyst synthesized by Co doping and ultrasonic exfoliation exhibited a broader absorption band edge. Next, an a-TiO2/Co-ZnIn2S4composite photocatalyst was successfully prepared by coating partly amorphous TiO2on the surface of Co-ZnIn2S4, and the effect of varying the TiO2loading time on photocatalytic performance was investigated. Finally, MoP was loaded as a co-catalyst to increase the hydrogen production efficiency and reaction activity of the catalyst. The absorption edge of MoP/a-TiO2/Co-ZnIn2S4was widened from 480 nm to about 518 nm, and the specific surface area increased from 41.29 m2/g to 53.25 m2/g. The hydrogen production performance of this composite catalyst was investigated using a simulated light photocatalytic hydrogen production test system, and the rate of hydrogen production by MoP/a-TiO2/Co-ZnIn2S4was found to be 2.96 mmol·h−1·g−1, which was three times that of the pure ZnIn2S4(0.98 mmol·h−1·g−1). After use in three cycles, the hydrogen production only decreased by 5%, indicating that it has good cycle stability.