Solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy has become a powerful tool for the investigation of local structure and medium range order in glasses. Previous P-31 MAS NMR studies have detailed the local structure for a series of phosphate glasses. Phosphate tetrahedra within the glass network are commonly described using the Q(sup n) notation, where n = 0, 1, 2, 3 and represents the number of bridging oxygens attached to the phosphate. Using P-31 MAS NMR different phosphate environments are readily identified and quantified. In this paper, the authors present a brief description of recent one dimensional (1D) Li-6, Li-7 and P-31 MAS experiments along with two-dimensional (2D) P-31 exchange NMR experiments for a series of lithium ultraphosphate glasses. From the 2D exchange experiments the connectivities between different Q(sup n) phosphate tetrahedra were directly measured, while the 1D experiments provided a measure of the P-O-P bond angle distribution and lithium coordination number as a function of Li2O concentration.