This work explores, for the first time, the stereoisomerism effect of sugar units of glycopolymers on hydrogelation. Three glycopolymers with an identical main chain but different pendent sugar stereoisomers are employed. Hydrogelation of the glycopolymers occurs driven by the dynamic covalent bonds between the sugar units and the benzoboroxole (BOB)-containing polymer. We conclude that the gelation ability of the glycopolymers differs obviously as shown in the sequence, Man > Gal > Glc due to the corresponding difference in their sugar-BOB interaction ability.