Hollow V2O5 spheres constructed from plate-like particles were synthesized. These materials exhibited a tremendous pseudocapacitance effect with a high capacitance of 479Fg−1 at 5mVs−1 when used as supercapacitor electrodes in a solution of 5M LiNO3. After the surface of hollow V2O5 spheres was coated with PPy, the composite electrode was formed and its electrochemical properties were also improved. This composite material exhibited the capacitances of 559Fg−1 at 3Ag−1 by GCD and 566Fg−1 at 5mVs−1 by CV, respectively. At the same time, the capacity retentions of 70% and 66% were respectively achieved even after 100 cycles.