Glycohydrogels containing 2 '-acrylamidoethyl-beta-d-galactopyranoside and varying levels of N,N ' methylene bisacrylamide and 3-acrylamidopropyltris(trimethylsiloxy)silane were synthesized to determine the effects of crosslinker and amphipathic balance on equilibrium water content (EWC), bound water population, and hydrogen bonding dynamics at the water-polymer interface. Analogous dimethylacrylamide hydrogels were synthesized for comparison with a system containing lower hydrogen bonding propensity. An approach combining experiment (proton nuclear magnetic resonance, thermogravimetric analysis, differential scanning calorimetry, and dynamic vapor sorption analysis) and molecular dynamics simulations was employed to examine the relationship between bulk hydrogel properties, molecular water mobility, and hydrogen bonding characteristics. It was found that copolymer composition (hydrophobic content) and crosslink concentration in high water content glycohydrogels affect EWC, and by extension, structural water population. The organization of water at the polymer interface is greatly impacted by the surrounding environment, where hindered molecular water mobility promotes water-polymer binding and decreases water-water clustering. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 584-597