Manganese dioxide may react with silicon tetrachloride to form manganese(Ⅳ) oxodichloride which reacts subsequently with another molecule of silicon tetrachloride leading to manganese tetrachloride eventually in chlorinated solvents. This in situ generated manganese(Ⅳ) oxodichloride or manganese tetrachloride were found to be very effective for the chlorination of a wide variety of alcohols to the corresponding chlorides. Primary, secondary and benzylic alcohols were converted into corresponding chlorides when treated with silicon tetrachloride in the presence of manganese dioxide at room temperature.