Direct chlorination of glycerol to dichloropropanol (DCP) was conducted in a liquid-phase batch rector using homogeneous H3PW12O40 heteropolyacid (HPA) catalyst. The effect of reaction conditions (reaction time, reaction pressure, reaction temperature, and catalyst amount) on the catalytic performance of H3PW12O40 in the direct preparation of DCP from glycerol was examined. The optimum reaction pressure and reaction temperature were found to be 10 bar and 130 oC, respectively. The reaction temperature was more crucial than the reaction pressure in improving the selectivity to DCP. Selectivity to DCP increased with increasing reaction time and with increasing catalyst amount. Acid sites of H3PW12O40 catalyst favorably devoted to the chlorination of glycerol. H3PW12O40 served as an efficient catalyst in the direct preparation of DCP from glycerol under the mild reaction conditions.