Poly (ethylene axide) (PEO) modified WO3 thin films were prepared on glass substrates with special temperature.The sol-gel transition proess was investigated by using DTA-TG,SEM and XRD.The electrochemical characteristic of the films was studied by cyclic voltmmetry measurement.The results show that PEO has heavy effects on the crystallization of WO3 during structure evolution because of the interaction between PEO and WO3.It increases the crystallization temperature of the gels and thus improves the electrochemical properties and cyclic life of WO3 film as electrochromic materials.