Reverse iodine transfer polymerizations (RITP) of 2-h-ydroxyethyl acrylate (HEA) were performed in N,N-dimethylformamide at 75 degrees C using AIBN as initiator. Poly(2-hydroxyethyl acrylate) (PHEA) with Mn = 3300 g mol-1 and Mw/Mn <1.5 were obtained. Homopolymerization of styrene in RITP was also carried out under similar conditions using toluene as solvent. The resulting iodo-polystyrene (PS-I) with (Mn, SEC = 607 g mol-1, polydispersity index (PDI) = 1.31) was used as a macroinitiator for the synthesis of amphiphilic block copolymers based on HEA with controlled well-defined structure. Poly(styrene-b-2-hydroxyethyl acrylate) (PS-b-PHEA) with Mn = 13,000 g mol-1 and polydispersity index (Mw/Mn) = 1.4 was obtained, copolymer composition was characterized using 1H-NMR and FTIR, whereas SEC and gradient HPLC were used to confirm the formation of block copolymer and the living character of polymer chains. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012