We report total energy calculations for different crystal structures of NaNbO 3 over a range of unit cell volumes using the all-electron full-potential (L)APW method. We employed both the local-density approximation (LDA) and the Wu-Cohen form of the generalized gradient approximation (GGA-WC) to test the accuracy of these functionals for the description of the complex structural behavior of NaNbO 3 . We found that LDA not only underestimates the equilibrium volume of the system but also predicts an incorrect ground state for this oxide. The GGA-WC functional, on the other hand, significantly improves the equilibrium volume and provides relative phase stability in better agreement with experiments. We then use the GGA-WC functional for the calculation of the phonon dispersion curves of cubic NaNbO 3 to identify the presence of structural instabilities in the whole Brillouin zone. Finally, we report comparative calculations of structural instabilities as a function of volume in NaNbO 3 and KNbO 3 to provide insights for the understanding of the structural behavior of K 1-x Na x NbO 3 solid solutions.2