The TiO2, MoO3, PEO doped four-member tungstic acid sols were prepared for the first time. The stability of different doped content sols were investigated and optimized with rotational viscometer. The four-member doped tungstic acid sol was very stable which could be stored more than two months at room temperature. The WO3 electrochromic film prepared from this doped four- member tungstic acid sol had excellent performance and longevity of service. The stability of different doped solders were investigated and optimized with rotational viscometer. The four-member doped tungstic acid sol was very stable which could be stored more than two months at room temperature. The WO3 electrochromic film prepared from this doped four- member tungstic acid sol had excellent performance and longevity of service.