The review deals with the chemistry of dimerization of acrylic esters in the presence of various catalysts. The article covers literature from 1963 through early 1995. The dimerization reactions are divided into three categories depending on the type of catalyst used, namely, phosphine-catalyzed, metal-catalyzed, and miscellaneous catalysts. Phosphine catalyzed dimerization leads to branched or head-tail dimers. Metal catalyzed dimerization deals with the reactions that take place in the coordination sphere of the transition metals (Ni, Pd, Ru, and Rh) complexes and are aimed at linear or tail-tail dimers. The tail-tail dimers, dialkyl hexenedioates, have a commercial potential as precursors of adipic acid, which is a raw material in the manufacture of nylon-6,6. Various strategies involved in designing the transition metal catalysts for tail-tail dimerization are highlighted. A miscellaneous catalyst section deals with systems that are not covered under the above two categories. It describes catalyst systems comprised of organic and/or inorganic compounds leading to head-tail or tail-tail dimers. The hydrodimerization reactions, which directly give dialkyl adipate from acrylic ester, are discussed separately. The mechanisms of the important dimerization reactions are outlined at appropriate places.