Silica gels composited with undecatungstochromoferrous acid have been prepared by the sol-gel method. FT-IR spectra and SEM declared that theKeggin structure characteristic of the Fe(H2O)CrW11O39 6−anionwas found in the silica gel skeleton. The change of characteristic peaks in IR spectra was analyzed. XRD pattern showed that the gel was amorphous. The gel exhibited considerably high-proton conductivity, which increased from 1.88×10−3 to 1.11×10−2 S cm−1 with the increase of the content of undecatungstochromoferrous acid at 20℃.