Comparative molecular dynamics simulations of n-octyl-β-d-galactopyranoside (β-C₈Gal) and n-octyl-β-d-glucopyranoside (β-C₈Glc) micelles in aqueous solution have been performed to explore the influence of carbohydrate stereochemistry on glycolipid properties at the atomic level. In particular, we explore the hypothesis that differences in T_m and T_c for β-C₈Gal and β-C₈Glc in lyotropic systems arise from a more extensive hydrogen bonding network between β-C₈Gal headgroups relative to β-C₈Glc, due to the axial 4-OH group in β-C₈Gal. Good agreement of the 13 ns micelle−water simulations with available experimental information is found. The micelles exhibit a similar shape, size, and degree of exposed alkyl chain surface area. We find net inter- and intra-headgroup hydrogen bonding is also similar for β-C₈Gal and β-C₈Glc, although n-octyl-β-d-galactopyranoside micelles do exhibit a slightly greater degree of inter- and intra-headgroup hydrogen bonding. However, the main distinction in the calculated microscopic behavior of β-C₈Glc and β-C₈Gal micelles lies in solvent interactions, where β-d-glucosyl headgroups are considerably more solvated (mainly at the equatorial O4 oxygen). These results agree with preceding theoretical and experimental studies of monosaccharides in aqueous solution. A number of long water residence times are found for solvent surrounding both micelle types, the largest of which are associated with surface protrusions involving headgroup clusters. Our simulations, therefore, predict differences in hydrogen bonding for the two headgroup stereochemistries, including a small difference in inter-headgroup interactions, which may contribute to the higher T_m and T_c values of β-C₈Gal surfactants relative to β-C₈Glc in lyotropic systems.