Selective interactions of ions with charge-neutral saccharides can have far-reaching consequences in biological and wet-technological contexts but have so far been observed only indirectly. Here, we directly quantify by total-reflection X-ray fluorescence the preferential accumulation of ions near uncharged saccharide surfaces in the form of glycolipid Langmuir monolayers at air/water interfaces exhibiting different levels of structural ordering. Selective interactions with ions from the aqueous subphase are observed for monolayers featuring crystalline ordering of the saccharide headgroups, as determined by grazing-incidence X-ray diffraction. The attracted ion species depend on the structural motifs displayed by the ordered saccharide layer. Our results may constitute a basis to understand the salt-specific swelling of wood materials and various phenomena in membrane biophysics.