Preparations of the highly ordered monoantennary, homofunctional diantennary, and heterofunctional diantennary neoglycopolymers of alpha-D-mannose and beta-D-glucose residues were achieved via ring-opening metathesis polymerization. Isothermal titration calorimetry measurements of these synthetic neoglycopolymers with Concanavalin A (Con A), revealed that heterofunctional diantennary architectures bearing both alpha-mannose and nonbinding beta-glucose units, poly(Man-Glc), binds to Con A (Ka = 16.1 x 10(6) M-1) comparably to homofunctional diantennary neoglycopolymer (Ka = 30 X 10(6) M-1) bearing only alpha-mannose unit, poly(Man-Man). In addition, poly(Man-Glc) neoglycopolymer shows a nearly 5-fold increasing in binding affinity compared to monoantennary neoglycopolymer, poly(Man). Although the exact mechanism for the high binding affinity of poly(Man-Glc) to Con A is unclear, we hypothesize that the alpha-mannose bound to Con A might facilitate interaction of beta-glucose with the extended binding site of Con A due to the close proximity of beta-glucose to alpha-mannose residues in the designed polymerizable scaffold.