The bromoester functionalized d-glucopyranoside acetals based on methyl α-d-glucopyranoside (MeαdGlu) or 2-(hydroxymethyl)phenyl-β-d-glucopyranoside (salicin) were prepared and used to initiate the controlled atom transfer radical copolymerization of glycidyl and methyl methacrylates in the presence of CuCl/dNbpy in anisole at 30 °C. The well-defined copolymers with sugar cores sheltered by two-, three-, four-, or six-polymethacrylate segments with various polymerization degrees (DParm = 15–70) and low dispersity indices (Ð = 1.15–1.30) were successfully synthesized.