The nano-Bi2WO6/reduced graphene oxide composite obtained by a simple hydrothermal reaction demonstrates a larger specific capacitance of 922 F/g at a charge and discharge currents of 3 A/g with longer cycle life. The As comparison, pristine Bi2WO6 nanoparticles have poor specific capacitance of 574 F/g at a charge and discharge currents of 2 A/g with weak cycle life. Though analyzing the Cyclic voltammetry curves, it is found that there are two oxidation reaction occurring in the materials: oxidation of Bi (III) to Bi (IV) and Bi (III) to Bi (V). The oxidation of Bi (III) to Bi (IV) is reversible while Bi (III) to Bi (V) will cause nonreversible destroy on structure. In this nano-Bi2WO6/reduced graphene oxide composite, graphene with well conductivity will enhance the electrically conducting as charge transfer channel, so that electrons will be transfer much faster in oxidation and most Bi (III) is oxidized to be Bi (IV) which ensure larger specific capacitance and long cycle life. This nano-Bi2WO6/reduced graphene oxide composite has application prospect in high-performance pseudo-capacitors.