Selenoglycosides are important starting materials in synthetic carbohydrate chemistry and play a role in biological interactions as well. Both aspects are influenced by the conformation around the glycosidic bond. Here, we present a combined experimental and computational approach to measure and evaluate nJ(77Se,1H) coupling constants for their use in conformational analysis. The measurements were carried out using a modified CPMG-HSQMBC pulse scheme which yields pure absorption antiphase multiplets to allow accurate determination of the nJXH values regardless of the size of the proton-proton couplings. Theoretical calculations were performed at the Second-Order Polarization Propagator Approach (SOPPA) level. Population-averaged values calculated for geminal and vicinal couplings are in a good agreement with experiment indicating an adequate theoretical level of the calculations. Experimental observations and computations alike have indicated that two-bond 77Se-1H couplings, 2J(77Se,1H), in a H1-C1-Se-X moiety are very sensitive to the torsion angle around the C1-Se-bond and will, therefore, be useful for conformational studies. Copyright © 2011 John Wiley & Sons, Ltd.