NMR methods provide a useful approach to structural analysis of glycans in their native aqueous environment. However, demands for experimental data are high, particularly if internal motions as well as structure are to be described. Data from traditional sources, such as NOEs, are also limited, making additional data from paramagnetic effects (PREs and PCSs), residual dipolar couplings (RDCs) and residual chemical shift anisotropies (RCSAs) especially valuable. This chapter reviews the theory behind these data types, as well as methods for data acquisition and interpretation. It also presents examples of application to both free glycans in solution and glycans bound to protein receptors.