Exploiting photocatalysts with environmental friendliness, noble-metal-free and high efficiency is a great challenge for photocatalytic hydrogen evolution. In this work, we synthesized a novel MoS2/rGO/Cd0.6Zn0.4S composite catalyst based on microsphere-structural polymer with highly efficient photocatalytic activity under visible light irradiation. The 5.0%MoS2/rGO/Cd0.6Zn0.4S exhibited the highest H-2 evolution rate of 11.7 mmol/h/g, which about 2.1 times higher than that without MoS2 and 4 times higher than that without PSGM. This superior photocatalytic activity, further demonstrated by the transient photocurrent responses and electrochemical impedance spectrum, was attributed to the effective separation of the photo-generated charge carriers promoted by the positive synergetic effect between the MoS2 and graphene. This study provided a promising approach to achieve high-efficiency H-2 evolution based on graphene and MoS2 without noble metals. (C) 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.