Alkene and alkyne functional polyester-based dendrimers of generation 1 to 4 have been prepared and reacted under free-radical conditions with 2-acetamido-2-deoxy-1-thio-β-D-glucose (GlcNAc-SH). As the alkene-dendrimers underwent the addition of one thiyl radical per ene group whereas each yne group of alkyne-dendrimers was saturated by two thiyl radicals, a collection of glycodendrimers with glycan density ranging from six to ninety-six GlcNAc per dendrimer was obtained. The recognition properties of the prepared glycodendrimers toward the wheat germ agglutinin (WGA) were evaluated by enzyme-linked lectin assay (ELLA). The eight glycodendrimers were excellent ligands showing IC50 values in the nanomolar range and relative potencies per sugar unit up to 2.27 e6 when compared to monosaccharidic GlcNAc used as monovalent reference. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014