Incorporation high-loading redox-active materials with small amounts of graphene is a general protocol to achieve high-performance catalysts. Herein, hierarchical MoS2-reduced graphene oxide nanosheet (denoted as MoS2-rGO nanosheets) hybrids with a loading of MoS2 as high as 94 wt% are synthesized. The obtained hierarchical MoS2-rGO nanosheets simultaneously integrate the structural and compositional design rationales for high-efficiency and durable electrocatalysts based on high weight ratio of MoS2 in hybrid composite, highly stable/conducting rGO, well-dispersed two-dimensional ultrathin MoS2-nanosheets, more exposed edge sites and micro/nano hierarchical structure. When evaluated as electrocatalysts for hydrogen evolution and oxygen reduction reactions, the hierarchical MoS2-rGO nanosheets demonstrates enhanced activity and excellent stability, promising their applications in MoS2 based electrochemical, photo-catalytic and photo-elecrocatalytic cells. (C) 2015 Elsevier B.V. All rights reserved.