A combination of X-ray and electron diffraction, electron microscopy and solid-state nuclear magnetic resonance (NMR) has been used to elucidate the structure and the ordering of Na2ZrO3. The diffraction data confirm a monoclinic crystal structure. A sample prepared by a conventional solid-state reaction of the components is shown by both X-ray diffraction and electron microscope imaging to have an extremely high concentration of planar defects associated with stacking disorder of the planes along the c-axis. The incidence of these defects is significantly reduced in a sample recrystallised from a bismuth oxide flux. NMR indicates that the local coordinations are well defined in both samples but with some sharpening of the spectra from the recrystallised sample indicative of the increase of long-range order. The 23Na magic angle spinning (MAS) NMR spectra clearly show three distinct sites with widely differing quadrupolar interaction parameters that can be related to the known site symmetries. Two distinct oxygen resonances are observed in the MAS NMR spectrum from an 17O-enriched sample while the static 91Zr NMR spectrum can be simulated with one set of interaction parameters.