Atom transfer radical polymerization (ATRP) has been employed in the polymerization of 2-methoxyethyl acrylate (MEA) initiated by ethyl 2-bromoisobutyrate in bulk or in toluene solution at 9095 degrees C with the catalytic systems Cu(I)Br/PMDETA or HMTETA. Kinetics investigations revealed that ATRP of MEA proceeds in a controlled manner with a first-order plot of monomer consumption, an almost linear molecular weight evolution and polydispersities < 1.29 in the entire conversion range. Well-defined diblock copolymers with PMMA, PMEA-b-PMMA have been produced by use of both PMEA and PMMA macroinitiators, however, for the latter the controlled conditions were somehow difficult to maintain. The amphiphilic behavior of the diblock copolymers lead to phase separation resulting in two glass transition temperatures as detected by DSC. Contact angle (Theta) investigations with water on PMEA, PMMA, and diblock copolymers surfaces reveal PMEA as an intermediate hydrophilic with Theta similar to 50 degrees, whereas PMMA and the diblock copolymers all fall in the hydrophobic region with Theta > 70 degrees. (c) 2006 Wiley Periodicals, Inc.