Methyl alpha- and beta-pyranosides of D-glucose and D-galactose 1-4 were prepared containing single sites of C-13-enrichment at C4, C5, and C6 (12 compounds), and H-1 and C-13{H-1} NMR spectra were obtained to determine a complete set of J-couplings ((1)J, (2)J, and (3)J) involving the labeled carbon and nearby protons and carbons within the exocyclic hydroxymethyl group (CH2OH) of each compound. In parallel theoretical studies, the dependencies of (1)J, (2)J, and (3)J involving H-1 and C-13 on the C5-C6 (omega) and C6-O6 (theta) torsion angles in aldohexopyranoside model compounds were computed using density functional theory (DFT) and a special basis set designed to reliably recover the Fermi contact contribution to the coupling. Complete hypersurfaces for (1)J(C5,C6), (2)J(C5,H6R), (2)J(C5,H6S), (2)J(C6,H5), (2)J(C4,C6), (3)J(C4,H6R), (3)J(C4,H6S), and (3)J(C6,H4), as well as (2)J(H6R,H6S), (3)J(H5,H6R), and (3)J(H5,H6S), were obtained and used to parametrize new equations correlating these couplings to omega and/or theta. DFT-computed couplings were also tested for accuracy by measuring J-couplings in C-13-iabeled 4,6-O-ethylidene derivatives of D-glucose and D-galactose in which values of omega and theta were constrained. Using a new computer program, Chymesa, designed to utilize multiple J-couplings sensitive to exocyclic CH2OH conformation, the ensemble of experimental couplings observed in 1-4 were analyzed to yield preferred rotamer populations about omega and theta. Importantly, due to the sensitivity of some couplings, most notably (2)J(H6R,H6S), (2)J(C5,H6R), and (2)J(C5,H6S), to both omega and theta, unique information on correlated conformation about both torsion angles was obtained. The latter treatment represents a means of evaluating correlated conformation in 1,6-linked oligosaccharides, since psi and theta are redundant in these linkages. In the latter regard, multiple, redundant scalar couplings originating from both sides of the glycosidic linkage can be used collectively to evaluate conformational correlations between psi/theta and C5-C6 bond rotamers.