Carboxyl- and hydroxyl-terminated dithiocarbamates and xanthates were practically synthesized. Carboxyl- and hydroxyl-terminated polymers were made from them. These reversible addition-fragmentation chain transfer (RAFT) agents had low chain-transfer constants that resulted in wider molecular distributions for the polymers. Nevertheless, kinetic studies showed that the polymerization behaved like a RAFT-mediated process after a fast start. H-1 NMR and matrix-assisted laser desorption/ionization spectra confirmed that the functional group or groups were cleanly transferred to the polymer end or ends. The copolymerization of methacrylates and acrylates could bring the former under control during radical polymerization. Block copolymers were synthesized through the condensation of the functional polymers with other types of functional polymers or through the condensation of the functional agents followed by radical polymerization. (c) 2006 Wiley Periodicals, Inc.