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Poly ethylene oxide(PEO)x-V2O5-MoO3(x=0,0.5,1) films were prepared by the sol-gel method.The synthesis and structure of the films were investigated by XRD,TG-DTA,FTIR,etc.The results show that V2O5-MoO3 xerogel has a layered structure and its interlayer space increased from 1.3181nm at x=0 to 1.7898nm at x=1 after the nanocomposite films were dried,and PEO in the interlayer changes the interface structure by forming hydrogen bonds with V=O bands.CV measurement indicates that the intercalation of PEO improves insertion/extration properties of Li+ ions in the interlayer.