In this study, poly(ethyleneoxide) and poly(ethylene imine) polymer blends containing fumed silica fillers were studied in order to enhance the ion conductivity and interfacial properties. Lithium perchlorate (LiClO4) as a salt, and silica(SiO2) as the inorganic filler were introduced into the polymer composite electrolyte composites and the composites were examined to evaluate their ionic conductivity for a possibility test of electrolyte application. As the diameter of semicircle in an impedance test became smaller, ionic conductivity of composite electrolytes had been enhanced by addition of 20 wt% silica filler. However, the conductivity was not greatly changed over 20 wt% content because the silica was sufficiently saturated in the polymer electrolytes. Diffraction peaks of PEO became weaker with the addition of inorganic fillers using XRD analysis. It showed that a crystallinity was proportionally reduced by increasing filler contents. The morphology of composite electrolyte films has been investigated by SEM. The heterogeneous morphology which silica was evenly dispersed by the strong adhesion of PEI was shown at higher contents of silica.