The two studies presented here demonstrate that nanoES-FT-ICR MS is a powerful method for studying the association of oligosaccharide ligands with monomeric and multimeric proteins. It permits the facile identification of the occupancy of binding sites, information that is not readily available by other techniques. Its high-resolution capability is ideally suited to the observation of interactions between a large protein receptor and a relatively small oligosaccharide ligand. The sensitive and rapid determination of association constants for protein carbohydrate complexes is expected to find wide application.