A method of preparing chlorohydrins, the method comprising: introducing a polyhydroxy aliphatic hydrocarbon comprising 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, a catalyst which is an 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, a propionic acid, and a chlorination agent into a first reactor in which the temperature is maintained in a range of 50 to 200 °C, wherein the polyhydroxy aliphatic hydrocarbon contains two or more hydroxyl groups bonded to different carbon atoms; discharging an effluent of the first reactor comprising water as a by-product from the first reactor; introducing at least a portion of the effluent of the first reactor effluent into a water removal device; and introducing the effluent of the first reactor from which water is removed and which includes an intermediate product as a reaction product of the catalyst, acting as a catalyst in a chlorination reaction of the polyhydroxy aliphatic hydrocarbon, and an additional chlorination agent into a second reactor in which the temperature is maintained in a range of 80 to 200 °C, wherein the effluent of the first reactor introduced into the water removal device comprises polyhydroxy aliphatic hydrocarbon, chlorohydrins, and said intermediate product as a reaction product of the catalyst and the polyhydroxy aliphatic hydrocarbon at a ratio of 0 to 90 parts by weight of the polyhydroxy aliphatic hydrocarbon: 5 to 95 parts by weight of the chlorohydrins: 5 to 12 parts by weight of the intermediate product, and 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 device forms an azeotropic mixture, without further adding a catalyst other than the catalyst and the intermediate product from the first reactor into the second reactor, and the water removal device is operated by distillation operation based on a boiling point difference between constituents of the reaction mixture added to the water removal device. introducing a polyhydroxy aliphatic hydrocarbon comprising 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, a catalyst which is an 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, a propionic acid, and a chlorination agent into a first reactor in which the temperature is maintained in a range of 50 to 200 °C, wherein the polyhydroxy aliphatic hydrocarbon contains two or more hydroxyl groups bonded to different carbon atoms; discharging an effluent of the first reactor comprising water as a by-product from the first reactor; introducing at least a portion of the effluent of the first reactor effluent into a water removal device; and introducing the effluent of the first reactor from which water is removed and which includes an intermediate product as a reaction product of the catalyst, acting as a catalyst in a chlorination reaction of the polyhydroxy aliphatic hydrocarbon, and an additional chlorination agent into a second reactor in which the temperature is maintained in a range of 80 to 200 °C, wherein the effluent of the first reactor introduced into the water removal device comprises polyhydroxy aliphatic hydrocarbon, chlorohydrins, and said intermediate product as a reaction product of the catalyst and the polyhydroxy aliphatic hydrocarbon at a ratio of 0 to 90 parts by weight of the polyhydroxy aliphatic hydrocarbon: 5 to 95 parts by weight of the chlorohydrins: 5 to 12 parts by weight of the intermediate product, and 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 device forms an azeotropic mixture, without further adding a catalyst other than the catalyst and the intermediate product from the first reactor into the second reactor, and the water removal device is operated by distillation operation based on a boiling point difference between constituents of the reaction mixture added to the water removal device.