The synthesis and characterization of a series of glycopolymer brushes with P(methyl 6-O-methacryloyl-a-D-glucoside) (P(6-O-MMAGIc)) side chains (SCs) is reported. The formation of well-defined glycopolymer brushes is confirmed by 1H NMR spectroscopy and size exclusion chromatography (SEC) with a MALLS detector. Four multifunctional macroinitiators with different topologies and molar masses are prepared. The P(6-O-MMAGIc) SCs are cleaved from the backbone and analyzed by 1H NMR and SEC–MALLS, which further confirmed the synthesis of well-defined glycopolymer brushes. The grafting efficiency of P(6-O-MMAGIc) from the different macroinitiators are determined to be in the range 0.37 <f <0.55.