The 13C NMR T l relaxation times for the (1 ~ 4)-linked maltooligomers (M i) and the (1 -, 6)-linked isomaltooligomers (IM i) with i = 2, 4, 6, and 8 were measured in aqueous solution at 22 and 65Β°C at a concentration (3%) low enough to have removed concentration-dependenl effects on the measured T~ values. Separate T~ values were measured for each carbon in the residue at the reducing end of the oligosaccharide, in the residue at the non-reducing end, and in the interior, i.e., non-terminal, residue(s). Analogous data for the corresponding high polymers show that at 22Β°C the relaxation times for the carbons of the interior residues of the oligomers haw: converged to their high chain length asymptotes at about i = 10. This observation suggests that at room temperature polymeric motions in the frequency domain effective for ~3C NMR relaxation at a magnetic field strength of 11.7 T have a "wavelength" of the order of 10 residues. The relaxation times characterizing the two ends of the chain are different, with longer T l values for the carbons of the reducing end than for those of the non-reducing end. Carbons of a-anomeric residues at the reducing end have shorter relaxation times than those of the corresponding /3-anomeric reducing sugars. Carbons of the interior residues have T I values shorter than the carbons of either type of terminal residue. For oligomers of a given dp there is no T~ difference between oligomers of the M i and IM i series at room temperature. This observation is seemingly at odds with the great differences in the inherent conformational freedom of the (1 ~ 4)-and (1 -~ 6)-linkages. At elevated temperatures the orientational relaxation behavior of the two series of oligomers measured by 13C T 1 values show interesting differences, and in the case of the M, series, structure develops in the chain length dependence of the T l values.