In this study, the polymerization of (2-hydroxyethyl) acrylate (HEA), in polar media, using Cu(0)-mediated radical polymerization also called single-electron transferliving radical polymerization (SET-LRP) is reported. The kinetics aspects of both the homopolymerization and the copolymerization from a poly(ethylene oxide) (PEO) macroinitiator were analyzed by 1H NMR. The effects of both the ligand and the solvent were studied. The polymerization was shown to reach very high monomer conversions and to proceed in a well-controlled fashion in the presence of tris[2-(dimethylamino)ethyl]amine Me6-TREN and N, N,N', N?, N?-pentamethyldiethylenetriamine (PMDETA) in dimethylsulfoxide (DMSO). SET-LRP of HEA was also led in water, and it was shown to be faster than in DMSO. In pure water, Me6-TREN allowed a better control over the molar masses and polydispersity indices than PMDETA and TREN. Double hydrophilic PEO-b-PHEA block copolymers, exhibiting various PHEA block lengths up to 100 HEA units, were synthesized, in the same manner, from a bromide-terminated PEO macroinitiator. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012