Graft copolymers with poly(ethylene oxide) (PEO) side chains were prepared by atom transfer radical copolymerization (ATRP) of NAP-dimethylacrylamide (DMAA) with PEO macromonomer functionalized by methacrylate group (PEOMA). The reactions were initiated by alkyl halides in the presence of CuBr/HMTETA or CuCl/Me6TREN catalyst/ligand complexes in organic solvents at 70 or 30 degrees C. The well-defined graft copolymers with polymerization degree up to 100 repeating units in the backbone and molecular weight distribution in the range 1.1-1.4 were obtained. Reactivity ratio of PEO methacrylate was higher in comparison to DMAA yielding copolymers with spontaneous gradient. Amorphous morphology was observed for DMAA/PEO copolymers with shorter PEO chains (n(EO) = 5), whereas introduction of macromonomer having longer chain of PEO (n(EO) = 23) generated crystalline properties. (C) 2007 Elsevier Ltd. All rights reserved.