Abstract: The ring cleavage reaction between polyacetoxysilanes and epichloro-hydrin using 5-tert-butyl-2-furanatochromium(Ⅲ) as a catalyst was studied in detail and the corresponding products containing both acetoxy and substituted isopropoxy groups were obtained. The distribution of the products of the reaction depended on the molar ratio between polyacetoxysilanes and epichlorohydrin. IR of the products showed that the reaction between the reagents was stepwise; after the first acetoxy group reacted with the epichlorohydrin, the second and third acetoxy groups with subsequent mole of epichlorohydrin successively.