•Graphene/V2O5 xerogels nanocomposites were synthesized by a hydrothermal method.•Two-dimensional graphene sheet provided a sheet-on-sheet (V2O5/graphene) nanostructure and a large contact interface.•Graphene enhanced the electronic conductivity of V2O5 xerogels.•The graphene/V2O5 xerogels nanocomposites exhibited excellent rate capability.The graphene/V2O5 xerogels nanocomposites were synthesized by the hydrothermal method. The structure of the samples was characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The electrochemical properties of the graphene/V2O5 xerogels nanocomposites were studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge–discharge measurements as electrode materials for supercapacitor. In the graphene/V2O5 xerogels nanocomposites, graphene sheets and the layers of V2O5 xerogels (V2O5 · 1.6H2O) were stacked together. The graphene/V2O5 xerogels nanocomposites exhibited high specific capacity and high-rate capability, delivering a specific capacitance of 195.4 F/g and 184.6 F/g at the current density of 1A/g and 10 A/g between 0 and 0.65 V, respectively.