Micro–nanosized vanadium pentoxide (V2O5) was synthesized by hydrothermal reduction of amorphous V2O5, followed by thermal treatment in air atmosphere. Pyrrole was in-situ polymerization on the surface of V2O5 to obtain V2O5@PPy hybrid material.The as-synthesized V2O5 with about 100 nm in diameter and several hundreds nanometers in length were obtained and PPy layer with about 100 nm in thickness coated on the surface of V2O5. Electrochemical measurement showed that V2O5@PPy hybrid material had improved lithium storage ability and cycling performance compared with pure V2O5. PPy modification supplied a new route to obtain V2O5 hybrid cathode with significantly improved cyclic performance and showed promising applications in recharged lithium batteries.