The relationship between polyol adsorption affinity and silanol defect density was investigated through the development of vapor and aqueous adsorption isotherms on silicalite-1 materials which vary in structural and surface properties. Silicalite-1 crystals prepared through alkaline synthesis, alkaline synthesis with steaming post-treatment, and fluoride synthesis routes were confirmed as crystalline mordenite framework inverted (MFI) by SEM and XRD and were shown to contain similar to 8.50 silanol defects per unit cell by Si-29 MAS, H-1 MAS, and (HSi)-H-1-Si-29 CPMAS NMR. A hysteresis in the Ar 87 K adsorption isotherm at 10(3) P/P-0 evolved with a decrease in silanol defects, and, through features in the XRD and Si-29 MAS NMR spectra, it is postulated that the hysteresis is the result of an orthorhombicmonoclinic symmetry shift with decreasing silanol defect density. Gravimetric and aqueous solution measurements reveal that propylene glycol adsorption at 333 K is promoted by silanol defects, with a maximum 20-fold increase observed for aqueous adsorption at similar to 10(-3) g/mL with an increase from similar to 0 to 8.5 silanols per unit cell. A comparison of vapor and aqueous propylene glycol adsorption isotherms on defect-free siicalite-1 at 333 K, both of which exhibit the Type-V character, indicates that water. enhances adsorption by a factor of similar to 2 in the Henry's Law regime. Henry's constants for aqueous C-2-C-4 polyol adsorption (concentrations below 0.004 g/mL) at 298 K are shown to have a linear dependence on the silanol defect density, demonstrating that these molecules preferentially adsorb at silanol defects at dilute concentrations. This systematic study of polyol adsorption on silicalite-1 materials highlights the critical role of defects on adsorption of hydrophilic molecules and clearly details the effects of coadsorption of water, which can guide the selection of zeolites for separation of biomass-derived oxygenates.