The heterogeneous esterification reaction of acrylic acid with hexanol over three different cation-exchange resins, Amberlyst 131, Amberlyst 15, and Dowex 50Wx-400, was investigated. Surface area, pore volume, average pore diameter, and acid capacity analyses were carried out for these three catalysts. Amberlyst 131 gave the highest conversion, and therefore, further experiments were performed catalyzed by Amberlyst 131. The absence of external and internal mass transfer resistances was investigated for the esterification of acrylic acid with hexanol. Experiments showed that the reaction is controlled by chemical step rather than external and internal mass transfer steps. The effects of temperature, catalyst loading, and alcohol to acid molar ratio on the conversion of acrylic acid were determined. The activation energy and kinetic and adsorption constants were determined according to the Langmuir-Hinshelwood-Hougen-Watson mechanism.