The covalent immobilization of suitable alkyne/azide carbohydrate derivatives on complementarily functionalizated azide/alkyne silica was performed by click ligation througth the Cu(I)-catalyzed 1,3-dipolar cycloaddition reaction of such compounds. The new glyco-silicas have shown to be efficient and valuable bio-selective affinity chromatographic supports for the purification of lectins as well as for the one-pot fluorescent labeling of those proteins. The synthetic methodology is simple, high yielding and flexible, allowing the preparation of tailored glyco-silicas with potential future applications in the inmobilization of other biomolecules.