Despite the vast molecular diversity of glycans, we face common, and often interconnected, challenges in their NMR structural studies, namely: 1) discrimination of distinct conformations amongst a conformation-rich landscape, 2) limited structural data for more reliable molecular modeling and 3) spectral overlap, especially observed for homopolymers. We have attempted to address these issues by improving sensitivity and spectral resolution, though both cannot be simultaneously achieved. We will show that labile 1H signals can help alleviate two of these challenges increase the repertoire of structural data available and provide a path to discriminate potentially “biologically active” conformations and to improve the quality of both, the acquired data and the derived structural models. We will also present our ongoing efforts to enhance the spectral resolution to enable the structural studies of larger homo- and hetero-oligosaccharides.