AbstractSeveral acrylic esters were polymerized with radical and anionic initiators and the stereoregularity of the polymers was determined. The radical polymerization oftert‐butyl acrylate gave syndiotactic‐rich polymers at low temperatures as did isopropyl and trimethylsilyl acrylates. A radically obtained polymer of triphenylmethyl acrylate was atactic in contrast to poly(triphenylmethyl methacrylate). In the anionic polymerization with phenylmagnesium bromide or butyllithium as catalyst, the stereoregularity of the polymers was governed by the coordination of the catalyst which depends on the polarity and bulkiness of ester groups, the polarity of solvents, and the temperature in the polymerizat