The nanocomposite films were prepared by poly(ethylene oxide), PEO, intercalation in V2O5 xerogel in sol-gel. The synthesis and state of the films are in vestigated by the XRD, IR, SEM, etc. The results show that V2O5 xerogel is a layered structure which arranges in c-direction. The interlayer distance of V2O5 xerogel increases remarkably when PEO is intercalated in V2O5 xero gel interlayer. PEO has strong interaction with V2O5 host. The surface of the films is homogeneous without holes and cracks.