In this paper, novel star glycopolymers were synthesized via Cu(0)-mediated radical polymerisation at ambient temperature. The reaction was fast with little star–star coupling. Moreover, star glycopolymers can be obtained without removing oxygen from the polymerisation mixture. The effects of solvent and the ratio of initiator/catalyst/ligand on polymerisation were investigated, and the optimal conditions for the synthesis of star glycopolymer were determined. In addition, the binding ability between synthesised glycopolymers and concanavalin A (ConA) was studied using a turbidity test and quartz crystal microbalance-dissipation (QCM-D). Compared with linear glycopolymers, star glycopolymers showed higher binding ability to specific lectins and the strongest binding was obtained when the molecular weight was medium.