The amorphous V 2O 5 films prepared by vacuum evaporation are unstable and easily dissolved by electrolyte during the electrochromic process, so unfit to make electrochromic materials. We found that the annealed films have enhanced stability and electrochromic properties. We studied the microstructural changes during the electrochromic process by Raman spectra and discussed the mechanism for the enhancement. The results indicated that the amorphous films annealed by 400-500℃became polycrystalline and the films contained (V 2O 5)n ordered chains which prevented the films from solution effectively and enhanced the electrochromic characteristics. When colored and decolored, the microstructure of the polycrystalline V 2O 5 films changed inversely. During the cathodic polarization process, Li+inserted into the V 2O 5 crystal cell , formed V-O-Li band, disordered the films and UV absorption of the films blue shifted. On the contrary , during the anodic polarization process, Li +escaped from the crystal cell. The films largely restored .