A variety of crystalline alkali molybdate phases are characterized by Na-23, Cs-133, and Mo-95 magic-angle-spinning nuclear magnetic resonance (MAS NMR) to provide spectroscopic handles for studies of devitrification products in borosilicate nuclear waste glasses. The NMR parameters obtained from line-shape simulations are plotted as a function of various structural parameters to discern trends that may prove useful in the determination of unknown phases. These are applied to Cs3Na(MoO4)(2), the most common precipitate found in cesium- and molybdenum-bearing model nuclear waste glasses, the crystal structure of which has determined, to provide structural constraints that may guide the refinement of powder X-ray diffraction data.