The atom transfer radical polymerization of an unprotected glycomonomer, 2-{[(D-glucosamin-2N-yl)carbonyl]-oxy}ethyl methacrylate (HEMAGI) is firstly reported. Controlled polymerizations were performed with the CuBr/N,N,N',N',N'-pentamethyldiethylene triamine catalytic system with ethyl 2-bromoisobutyrate and 1,2-bis(bromoisobutyryloxy) ethane as mono and difunctional initiators in DMF solutions (80% w/w) at 40 and 50 degrees C, respectively. The polymerization of HEMAGI resulted in a controlled polymerization with linear kinetics, molecular weights which increase with conversion and narrow polydispersity indexes. Mono and difunctional PHEMAGI macroinitiators were used to synthesize the amphiphilic di and triblock glycopolymers with n-butyl acrylate, verifying their living character. The self-assembly of these glycopolymers in distilled water and in 0.1 M NaCl solutions was studied by dynamic light scattering, showing the role of hydrogen bonds and the hydrophobic parts. In addition, their interaction with Concanavalin A lectin was examined, demonstrating the influence of molecular weight and copolymer composition. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3623-3631, 2010