The layered structure stability of bulk vanadyl phosphate dihydrate (VOPO4·2H2O) is investigated by using a deintercalation-intercalation reaction process involving short-range swelling, its basal spacing can be reversibility controlled and the layered structure can be maintained to above 400°C. By using delaminated vanadyl phosphate (VOPO4) nanosheets in 2-propanol, VOPO4/reduced graphene oxide (RGO) hybrid electrode materials for supercapacitor with different mass ratios of VOPO4 nanosheets to graphene oxide (GO) nanosheets have been prepared based on a nanosheet reassembling reaction between the exfoliated VOPO4 nanosheets and GO nanosheets and followed by calcinating in a tubular furnace at 400°C for 3 h under N2 atmosphere, and their electrochemical properties are systematically investigated by cyclic voltammetry and galvanostatic charge-discharge in 0.5M K2SO4 electrolyte. The VOPO4/RGO hybrid electrode with a mass ratio of VOPO4/RGO=1 exhibits a high specific capacitance of 378Fg−1 at a scan rate of 5mVs−1 with a good rate capability. This method broadens the application filed of VOPO4 nanosheets, and also supplies promising electrode candidates for supercapacitor.