AB block copolymers of 2-(2',3',4',6'-tetra-O-acetyl-beta-D-glucopyranosyloxy)ethyl acrylate (AcGEA) with styrene (St) have been synthesized by atom transfer radical polymerization using well-defined bromo-terminated polystyrene as a macroinitiator. An O-deacetylation of the precursor copolymers affords amphiphilic block copolymers, PSt-b-PGEA, with well-defined glycopolymer segments and narrow molecular weight distributions ((M) over bar(w)/(M) over bar(n) < 1.4). The examination of the aqueous solution of these amphiphilic block copolymers revealed the formation of ordered aggregates.