The NMR interactions of crystalline phases in the system Na2O-ZrO2-SiO2 have been studied by a combination of static and magic angle spinning NMR methods for the first time. A full multinuclear (17O, 23Na, 29Si and 91Zr) approach has been employed that allows the phases to be clearly identified. NMR interactions such as 29Si isotropic chemical shift correlate with the known structural units present. For 23Na the the different sites can often be distinguished on the basis of differing quadrupolar interactions.