A method of preparing chlorohydrins, the method comprising: introducing polyhydroxy aliphatic hydrocarbon, a catalyst, and a chlorination agent 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; introducing at least a portion of the effluent of the first reactor into a water removal device; 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; and introducing at least a portion of an effluent of the second reactor into a device for purifying chlorohydrins to obtain a concentrate of chlorohydrins, wherein in the first reactor, a reaction product of the catalyst and the polyhydroxy aliphatic hydrocarbon is formed as an intermediate product, and the intermediate product acts as a catalyst in a chlorination reaction of the polyhydroxy aliphatic hydrocarbon, wherein the polyhydroxy aliphatic hydrocarbon includes 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, wherein the catalyst comprises an organic acid catalyst, the organic acid catalyst including at least one compound selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, a polycarboxylic acid, a malonic acid, a levulinic acid, a citric acid, a succinic acid, and a propionic acid, wherein the water removal device is a distillation column, characterized in that the effluent of the first reactor introduced into the water removal device includes 10 to 25 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 forms an azeotropic mixture. introducing polyhydroxy aliphatic hydrocarbon, a catalyst, and a chlorination agent 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; introducing at least a portion of the effluent of the first reactor into a water removal device; 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; and introducing at least a portion of an effluent of the second reactor into a device for purifying chlorohydrins to obtain a concentrate of chlorohydrins, wherein in the first reactor, a reaction product of the catalyst and the polyhydroxy aliphatic hydrocarbon is formed as an intermediate product, and the intermediate product acts as a catalyst in a chlorination reaction of the polyhydroxy aliphatic hydrocarbon, wherein the polyhydroxy aliphatic hydrocarbon includes 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, wherein the catalyst comprises an organic acid catalyst, the organic acid catalyst including at least one compound selected from the group consisting of a monocarboxylic acid, a dicarboxylic acid, a polycarboxylic acid, a malonic acid, a levulinic acid, a citric acid, a succinic acid, and a propionic acid, wherein the water removal device is a distillation column, characterized in that the effluent of the first reactor introduced into the water removal device includes 10 to 25 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 forms an azeotropic mixture.