Polyethylene oxide(PEO)-based solid composite polymer electrolyte(SCPE) may be used as electrolyte material in high energy density all solid lithium batteries.The SCPE films made from PEI-PEO-LiClO4-CA-NCA were prepared using a solution casting method when PEO was used as matrix,LiClO4 as Li+donor,polyethylene imine(PEI),citric acid(CA),inorganic nano-powder(NCA),were used as properties improver.The products were characterized by X-ray diffraction(XRD) and the electrochemical impedance spectra(EIS) of the SCPE had been measured.The results show that the additives decrease the crystallinity of the SCPE films,improve the conductivity of the PEO-based SCPE.The conductivity of the SCPEreached 5×10-4 S·cm-1(25 ℃),while retaining a good mechanical strength and flexibility.