95Mo magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy is surprisingly sensitive to the local environment of tetrahedral molybdate species. A series of compounds related to expected crystallization products in nuclear waste glasses are probed to calibrate their spectral characteristics. Glasses formed with fast and slow quenching show a glassy peak corresponding to tetrahedral molybdate species. With slow quenching, a prominent sharp peak is observed, representing crystallinity. In sodium-borosilicate glasses with 2.5 mol% MoO3, the sharp peak corresponds to pure crystalline sodium molybdate. Cesium-sodium and lithium-sodium borosilicate glasses with Mo show crystalline peaks as well, and suggest that NMR may potentially be used to characterize mixed-cation molydates and more complex phase assemblages. While precise quantification of Mo in different phases is likely to be time-consuming, reasonable estimates can be obtained routinely, making 95Mo MAS NMR a useful tool for investigating phase separation and crystallization in model nuclear waste materials.