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 (³J_GH ) corroborate with the predicted dihedral angles.