H-ZSM-5 readily catalyzed the ring-opening of 1,2-epoxyalkane with alcohols to give alkoxy alcohols. The reaction proceeded accompanying the shape-selective properties of H-ZSM-5. The rate of the ring-opening was retarded by use of alcohols with larger numbers of carbon atoms such as hexanol. The selectivities for the substitution of nucleophile alcohols at the sterically more hindered position of the epoxide were improved to be almost higher than those under basic conditions.