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. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012