A samarium enolate, supported on a crosslinked polystyrene resin, successfully initiated the living anionic polymerization of allyl methacrylate (AMA) to afford the corresponding poly(AMA) with well-controlled molecular weights. Diblock, triblock, and tetrablock copolymerizations with methyl methacrylate (MMA) were also successfully performed. The formed polymers, supported on the resin by a benzyl ester linker, were quantitatively isolated from the resin by selective cleavage of the linker with trifluoroacetic acid (TFA). Allyl ester in the side chain was not affected by this isolation step. The allyl group of the immobilized poly(AMA-b-MMA) on the resin was transformed into a 2,3-dihydroxypropyl group by osmium oxidation. The resulting copolymer was isolated by TFA treatment of the resin, and it showed amphiphilicity. In both the polymerization and side-chain modification, the formed polymers were easily washed from excess reagents only by filtration, and this demonstrated the feasibility of the automated synthesis of functional polymers based on this solid-supported polymerization technique. (C) 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 853-860, 2003.