Iron oxide pillared clays (FeOx-pillared clays) such as FeOx-pillared hectorite and FeOx-pillared bentonitewere synthesized by the intercalation of iron (III) chloride into clay interlayers and calcined at 300◦C.The synthesized catalysts were utilized for styrene oxide ring opening by methanol, comparing with rawclays and Fe2O3. FeOx-pillared bentonite efficiently catalyzed the ring-opening of epoxides to produce-alkoxyalcohols in excellent yields under extremely mild reaction conditions. The quantitative yieldof 2-methoxy-2-phenylethanol was obtained using 30 wt% FeOx-pillared bentonite to styrene oxide at70◦C for 10 min. The optimized condition was applied to the ring opening of different epoxides such as1-dodecene oxide, cyclohexene oxide, butyl glycidyl ether, tert-butyl glycidyl ether and -pinene oxideto furnish the desired products in moderate to excellent yields.