Various aluminum chloride polymeric catalysts have been prepared by the reaction of anhydrous aluminum chloride with styrene-divinylbenzene copolymer bead in the carbon disulfide solvent. The shapes of aluminum chloride polymeric catalysts have been investigated by the use of optical microscope, scanning electron microscope and analysis of atomic absorption and electron microprobe X-ray. The catalytic effect of aluminurn chloride polymeric catalysts in the process of esterification of various organic acids with several aliphatic and aromatic alcohols have been studied.