(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs) were prepared by in-situ reaction, in which ethyl-orthosilicate (TEOS) was catalyzed by HC1 and NH3·H2O, respectively. The ionic conductivity, the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra, contact angle method and TEM. The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5 and 1.1×10-5 S/cm respectively at 30 ℃. The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2, and influences the surface energy and conductivity of CPE films directly. Meanwhile, the ionic conductivity is related to the surface energy.