Potassium carbonate reacts with silicon tetrachloride to form trichlorosilyloxy carbonylchloride which reacts subsequently with another molecule of silicon tetrachloride leading to phosgene eventually in chlorinated solvents. This in situ generated trichlorosilyloxy carbonylchloride or phosgene 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 potassium carbonate at room temperature.