prepared new glycoinitiators, based on methyl α‐d‐glucopyranoside (MeαdGlu) or 2‐(hydroxymethyl)phenyl‐β‐d‐glucopyranoside (salicin), in the presence of the catalyst system CuCl/dNbpy in anisole at 30 °C. The conditions were sufficient for successful synthesis of well‐defined copolymers with sugar cores sheltered by two‐, three‐, four‐, or six‐polymethacrylate segments with various polymerization degrees