AbstractA convenient method is described for the preparation of isotactic and syndiotactic poly(trimethylsilyl methacrylates) by using the monomer trimethyl silyl methacrylate and butyllithium initiation in toluene and tetrahydrofuran, respectively. The structure of these polymers enables complete hydrolysis to the corresponding poly(methacrylic acids), which were characterized with respect to tacticity and molecular weight. The asymmetric induction in toluene produced 89% isotactic polymer, while that in tetrahydrofuran gave polymer<90% syndiotactic and heterotactic in terms of triads. A method of fractionation of the polyelectrolytes by gel‐permeation chromatography on a preparative scale was shown to be applicabl