Living radical polymerization of 2-methoxyethyl acrylate (MEA) was achieved by single-electron-transfer/degenerative transfer mediated living radical polymerization (SET-DTLRP) in water catalyzed by sodium dithionate. The poly(2-methoxyethyl acrylate) is an amphiphilic polymer with a hydrophobic part (polyethylene chain) and a mildly hydrophilic tail. The plots of number-average molecular weight versus conversion and In{[M](0)/[M]} versus time are linear, indicating a controlled polymerization. This method leads to the preparation of alpha,omega-di(iodo) poly(2-methoxyethyl acrylate)s (alpha,omega-di(iodo)PMEA) macroinitiators that can be further functionalized. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right-angle light scattering (RALLS), a differential viscometer (DV) and refractive index (RI). The method studied in this work represents a possible route to prepare well-tailored macromolecules made of 2-methoxyethyl acrylate (biocompatible material) in an environmentally friendly reaction medium. To the best of our knowledge there is no previous report dealing with the synthesis of PMEA by any LRP approach in aqueous medium. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4454-4463, 2009