A novel rGO/V2O5 hybrid aerogel composite made up of vanadium pentoxide nanospheres embedded in graphene sheets was synthesized by an easy hydrothermal method. V2O5 with a loading of only 12 wt% in composite played a significant pseudocapacitance role. To obtain better material, an annealing process in a tube furnace was used. The final rGO/V2O5 electrode showed excellent electrochemical performance, achieving a specific capacitance of 384 F g-1 at 0.1 A g−1 and of 197 F g-1 at 2 A g−1. The rGO/V2O5 functioned as the anode and graphene functioned as the cathode in an asymmetric supercapacitor used in an organic electrolyte resulted in a wide potential operating window of 2.5 V and delivered a maximum energy density of 80.4 Wh kg−1 (275 W kg−1) at 0.2 A g−1. In addition, the device possessed acceptable cyclic stability, with only 17.8% loss after 10000 cycles at 2 A g−1. All of these outstanding properties could make the electrode material prepared in this study a promising application material for supercapacitors.