Well-defined di and triblock copolymers based on 2-hydroxyethyl methacrylate, HEMA, and n-butyl acrylate, BA, have been synthesized by atom transfer radical polymerization, ATRP. Two copolymers have been selected to prepare glycopolymers containing D-(+)-glucosamine or N-(4-aminobutyl)-D-gluconamide, NABG, by chemical modification of HEMA units. The chemical modification occurs by activation of the hydroxyl groups of the HEMA units with highly reactive p-nitrophenyl carbonate groups. The block copolymers structure and self-assembly have been comprehensively studied in solid state and in solution by differential scanning calorimetry, X-ray diffraction, atomic force microscopy and dynamic light scattering. The resulting glycopolymers obtained upon chemical modification turned out to be water soluble. Therefore, their carbohydrate-lectin interactions of have been analyzed by turbidimetry measurements. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 2565-2577, 2012