The esterification reaction of acrylic acid (AA) with 1,4-butanediol (BD) to produce 4-hydroxybutyl acrylate (HBA) was carried out in a batch reactive distillation mode over the Amberlyst 15 catalyst. The reactive distillation was highly desirable to increase the reaction rate of BD and eventually to obtain the high purity of HBA because the unreacted BD was not easily separable to the produced HBA after the reaction. The reaction pressure below 760 mm Hg was used to remove the by-product water from the reaction zone. The air-bubbling operation was successfully applied to prevent the polymerization of reactants and products under the vacuum condition (400 similar to 760 mm Hg). The reaction rates were strongly dependent on the reaction pressure, especially, the reaction rate of BD disappearance. The increased reaction rate of BD by the reactive distillation enabled to produce a high purity of HBA.