A series of polyimide/vanadium pentoxide (PI/V2O5) hybrid film has been successfully fabricated through the in situ formation of V2O5 within a polymer matrix by sol-gel process. The polyamic acid (PAA) is prepared from 4,4'-diaminodiphenyl ether (ODA) and 3,3,4,4'-benzophenonetetracarboxylic anhydride (BTDA) in N-methyl-pyrrolidinone (NMP) solvent. Then different amounts of Bis-(2,4-pentanedionato) vanadium oxide are incorporated into polyamic acid (PAA) matrix, respectively and then thermally imidized to form PI/V2O5 hybrid membranes. The imidization temperature and time are optimized by FTIR measurements through the observation of V2O5 absorption peak. The influence of V2O5 Content on the thermal stability, morphology and mechanical properties of PI/V2O5 hybrid films are studied.