Hard-sphere (HS) calculations predict three conformers for the branched B human blood group antigenic determinant (α LFuc(1 → 2)[α DGal(1 → 3)]βDGal) and two conformers for the linear tetrasaccharide (αLRha(1 → 2)αLRha(1 → 3)αLRha(1 → 3)βDGlcNAc), which constitutes a part of the repeating unit of the Shigellaflexneri O-antigen, which differ in conformational energy by less than 0.7 and 0.2 kcal/mol, respectively. However, a detailed 1H nmr study of specific interunit deshielding effects, quantitative treatment of spin-lattice relaxation times, and nuclear Overhauser enhancements requires that only one of the conformers thus predicted be, in fact, conformationally preferred in solution. These conformers are those predicted by hard-sphere exo-anomeric (HSEA) calculations.