A novel and simple approach to preparing hierarchical zinc oxide/reduced graphene oxide (ZnO/RGO@RGO) composite is demonstrated using few-layered graphene oxide (GO) and metal zinc as starting materials following combined processes, including in-situ metal zinc reduction and catalyzed GO deoxygenation. Metal zinc can directly reduce GO sheets in aqueous GO suspension at room temperature to obtain a porous composite precursor (ZnO/RGO) with ZnO nanoparticles anchored on the RGO sheets. Then another RGO protecting layer is directly coated on the ZnO/RGO precursor to obtain the hierarchical ZnO/RGO@RGO composite. In this step, the exposed ZnO nanoparticles on the surface of ZnO/RGO play the role of catalyst to accelerate the deoxygenation of GO from the extra added GO aqueous suspension under mild hydrothermal condition. The reaction mechanism of metal zinc with GO aqueous suspension has been explored and the catalyst role of ZnO has been verified in this work. The prepared ZnO/RGO@RGO composite exhibited both stable cycling performance and good rate capability as anode for lithium-ion batteries. The method to prepare ZnO/RGO composite is economic and eco-friendly, and the ZnO catalyzing GO reduction opens a new approach to prepare graphene derivates.