Three-dimensional (3D) molybdenum disulfide/reduced graphene oxide (MoS2/rGO) hydrogels were developed by a simple and controllable one-pot hydrothermal method. The MoS2 nanosheets were uniformly anchored on the 3D rGO framework with strong adhesion. The obtained MoS2/rGO hydrogel with optimized rGO percentage showed extremely high double-layer capacitance about 29.60 mF/cm(2) due to the special 3D network structure. Electrochemical measurements confirmed that the MoS2/rGO hydrogel exhibited excellent electrocatalytic activity for hydrogen evolution reaction (HER) with a small onset overpotential of 125 mV and Tafel slope of 41 mV/decade, indicating the Volmer-Heyrovsky mechanism during the HER process and the electrochemical desorption step as rate-limiting step. Our results demonstrated that the 3D MoS2/rGO hydrogel could not only provide rich active sites for HER due to the inhibition of re-stacking process of (0 0 2) planes of MoS2 nanosheets along the C-axis, but also greatly contribute to the enlarged electrochemical surface area because of the formation of 3D network structure in the self-assembly process. This may open up a potential way to design advanced materials for HER. (C) 2015 Elsevier Ltd. All rights reserved.