A solid-supported samarium enolate successfully initiated the polymerization of 2-(trimethylsilyloxy)ethyl methacrylate (TMS-HEMA) through the living anionic process. In addition, the silyl group was readily removed by treatment of the beads with a weak acid to afford the corresponding well-defined poly(methacrylate) having a hydroxyethyl group in the side chain (PHEMA). The hydroxyl group of the immobilized PHEMA on the beads was successfully acetylated to give poly(2-acetoxyethyl methacrylate), which could be quantitatively isolated from the beads by trifluoroacetic acid treatment. Moreover, the hydroxyl group of the immobilized PHEMA could be utilized as an initiator for acid promoted ring opening polymerization of lactone to yield the corresponding graft copolymer. In this method, the residual and excess reagents could be removed by filtration, which demonstrated the applicability of the present technique to a novel method for construction of functional polymers. (C) 2004 Wiley Periodicals, Inc.