Bis(cyclopentadienyl)zirconium dichloride catalyzed ring-opening reactions of epoxides derived from styrene, cyclohexene, norbornene and stilbene, in the presence of primary, secondary, tertiary, cyclohexyl, allyl and propargyl alcohols, resulted in the formation of beta-alkoxy alcohols in good to excellent yields with high regio- and stereoselectivity.