A method of preparing chlorohydrins, the method comprising: introducing polyhydroxy aliphatic hydrocarbon and a catalyst into a first reactor maintained at a temperature of 50 to 200 °C, wherein the polyhydroxy aliphatic hydrocarbon is a C 2 -C 20 compound having at least two hydroxyl groups bonded to different carbon atoms; discharging from the first reactor an effluent of the first reactor comprising water as a by-product; mixing at least a portion of the effluent of the first reactor with a chlorination agent and recirculating the resulting mixture to the first reactor; introducing into a water removal device a portion of the effluent of the first reactor which is not recirculated to the first reactor; and introducing the effluent of the first reactor from which water is removed, and an additional chlorination agent into a second reactor maintained at a temperature of 80 to 200 °C, wherein the effluent of the first reactor introduced into the water removal device comprises the chlorination agent and water at a ratio of 10 to 25.0 parts by weight of the total of the chlorination agent and the additional chlorination agent and 75 to 90 parts by weight of water so that the effluent of the first reactor introduced into the water removal step forms an azeotropic mixture; wherein a reaction product of the catalyst and the polyhydroxy aliphatic hydrocarbon is produced as an intermediate product in the first reactor, and the intermediate product acts as a catalyst in a chlorination reaction of the polyhydroxy aliphatic hydrocarbon; wherein the chlorination agent or the additional chlorination agent include a hydrogen chloride gas or an aqueous hydrochloric acid solution; wherein the polyhydroxy aliphatic hydrocarbon comprises at least one compound selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, glycerol, 1,2,4-butanetriol, 1,4-butanediol, and esters of these compounds; and wherein the catalyst is an organic acid catalyst selected from the group consisting of monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, malonic acid, levulinic acid, citric acid, succinic acid, and propionic acid, wherein the water removal device is a distillation column. introducing polyhydroxy aliphatic hydrocarbon and a catalyst into a first reactor maintained at a temperature of 50 to 200 °C, wherein the polyhydroxy aliphatic hydrocarbon is a C 2 -C 20 compound having at least two hydroxyl groups bonded to different carbon atoms; discharging from the first reactor an effluent of the first reactor comprising water as a by-product; mixing at least a portion of the effluent of the first reactor with a chlorination agent and recirculating the resulting mixture to the first reactor; introducing into a water removal device a portion of the effluent of the first reactor which is not recirculated to the first reactor; and introducing the effluent of the first reactor from which water is removed, and an additional chlorination agent into a second reactor maintained at a temperature of 80 to 200 °C, wherein the effluent of the first reactor introduced into the water removal device comprises the chlorination agent and water at a ratio of 10 to 25.0 parts by weight of the total of the chlorination agent and the additional chlorination agent and 75 to 90 parts by weight of water so that the effluent of the first reactor introduced into the water removal step forms an azeotropic mixture; wherein a reaction product of the catalyst and the polyhydroxy aliphatic hydrocarbon is produced as an intermediate product in the first reactor, and the intermediate product acts as a catalyst in a chlorination reaction of the polyhydroxy aliphatic hydrocarbon; wherein the chlorination agent or the additional chlorination agent include a hydrogen chloride gas or an aqueous hydrochloric acid solution; wherein the polyhydroxy aliphatic hydrocarbon comprises at least one compound selected from the group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol, glycerol, 1,2,4-butanetriol, 1,4-butanediol, and esters of these compounds; and wherein the catalyst is an organic acid catalyst selected from the group consisting of monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, malonic acid, levulinic acid, citric acid, succinic acid, and propionic acid, wherein the water removal device is a distillation column.