PEO modified TiO2-PEO organic-inorganic hybrid thin films were prepared via sol-gel dipping process on glass substrate pre-coated with ITO. The preparation parameters were studied. Electrochemical and optical properties of the films were characterized by cyclic voltammetric response and visible transmittance. X-ray diffraction (XRD) was used to determined the crystalline structure of the gel. The results show the sols added with PEO have acceptable stable periods for practical use. The PEO modified optical transitivity of the hybrid films has heavy effects on the crystallization of TiO2 during structural evolution because of the interaction between PEO and TiO2. PEO-　TiO2 films have better electrochemical activity than the TiO2 equivalent behaved as higher Li+ insertion/extraction current density and cyclic reversibility.