1H,1H,2H,2H-Heptadecafluorodecyl acrylate (AC8) was polymerized by reversible addition-fragmentation chain transfer and copolymerized with 2-hydroxyethyl acrylate with the formation of random and block copolymers, respectively. The kinetics of the (co)polymerization was monitored with H-1 NMR spectroscopy and showed that the homopolymerization and random copolymerization of AC8 were under control. As a result of this control and the use of S-1-dodecyl-S-(alpha,alpha'-dimethyl-alpha"-acetic acid)trithiocarbonate as a chain-transfer agent, the copolymer chains were end-capped by an a-carboxylic acid group. Moreover, the controlled polymerization of AC8 was confirmed by the successful synthesis of poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate)-b-poly(2hydroxyethyl acrylate) diblock copolymers, which were typically amphiphilic compounds. (c) 2006 Wiley Periodicals, Inc.