A novel purification route for alkyl methacrylate monomers has been developed. This new route takes advantage of trialkyl aluminums, which react with water and alcohols, to rigorously purify methacrylate monomers. Poly(alkyl methacrylates) can thus be synthesized using a wide variety of available monomers which under conventional purification procedures are not suitable for anionic polymerizations. Homopolymers with controlled molecular weights and fairly narrow molecular weight distributions have been synthesized anionically by taking advantage of the high purity of these polar monomers. Methacrylate-methacrylate block copolymers have also been synthesized with fairly narrow distributions and no detectable homopolymer contamination.