Interest in the structure and conformation of starch polysaccharides – having either academic or industrial motivation – is not diminishing. Aqueous solutions challange new experimental techniques. Results of high-field NMR measurements are reported related to maltooligomers. Unambiguous spectral assignments were obtained and it was found that all monomeric subunits have the 4C conformation. 13C relaxation times (T1) show remarkable flexibility (0.3 sec at 80°C). Minimization of non-bonded energy of helical segments of various lengths (up to DP 24) resulted in left-handed helical structures. Glycosidic carbon-proton coupling constants (3JGH ) corroborate with the predicted dihedral angles.