The valence state of uranium has been confirmed for the three sodium uranates (NaUO3)-O-V/[Rn](5f(1)), (Na4UO5)-O-VI/[Rn](5f(0)), and (Na2U2O7)-O-VI/[Rn] (5f(0)), using X-ray absorption near-edge structure (XANES) spectroscopy. Solid-state Na-23 magic angle spinning nuclear magnetic resonance (MAS NMR) measurements have been performed for the first time, yielding chemical shifts at -29.1 (NaUO3), 15.1 (Na4UO5), and -14.1 and -19 ppm (Na1 8-fold coordinated and Na2 7-fold coordinated in Na2U2O7), respectively. The [Rn]5f(1) electronic structure of uranium in NaUO3 causes a paramagnetic shift in comparison to Na4UO5 and Na2U2O7, where the electronic structure is [Rn] 5f(0). A Na-23 multi quantum magic angle spinning (MQMAS) study on Na2U2O7 has confirmed a monoclinic rather than rhombohedral structure with evidence for two distinct Na sites. DFT calculations of the NMR parameters on the nonmagnetic compounds Na4UO5 and Na2U2O7 have permitted the differentiation between the two Na sites of the Na2U2O7 structure. The linear thermal expansion coefficients of all three compounds have been determined using high-temperature X-ray diffraction: alpha(a) = 22.7 X 10(-6) K-1, alpha(b) = 12.9 X 10(-6) K-1, alpha(c) = 16.2 x 10(-6) K-1, and alpha(vol) = 52.8 X 10(-6) K-1 for NaUO3 in the range 298-1273 K; alpha(a) = 37.1 X 10(-6) K-1, alpha(c) = 6.2 X 10(-6) K-1, and alpha(vol) = 81.8 X 10(-6) K-1 for Na4UO5 in the range 298-1073 K; alpha(a) = 6.7 x 10(-6) K-1, alpha(b) = 14.4 X 10(-6) K-1, alpha(c) = 26.8 X 10(-6) K-1, alpha(beta) = -7.8 X 10(-6) K-1 and alpha(vol) = -217.6 x 10(-6) K-1 for Na2U2O7 in the range 298-573 K. The alpha to beta phase transition reported for the last compound above about 600 K was not observed in the present studies, either by high-temperature X-ray diffraction or by differential scanning calorimetry.