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 nano-meters 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.