The vaporization behavior and decomposition mechanism of NaUO3 were studied using Knudsen effusion mass spectrometry. The temperature dependence of the sodium partial pressure over the ternary phase field NaUO3-Na2U2O7-UO2 was measured for the first time: log(P-Na/Pa) = 10.98(+/- 0.04)-14,999(+/- 50)/(T/K). The enthalpy of formation of alpha-Na2U2O7 was moreover derived from second law analysis of the data at Delta H-f(m)o (alpha-Na2U2O7, C-Gamma, T = 298.15 K) = -(3208.4 +/- 5.5) kJ . mol (1), in very good agreement with the value reported in the literature from solution calorimetry. The existence of three polymorphs for Na2U2O7 (alpha, beta, and gamma) was confirmed using high temperature X-ray diffraction. The two phase transitions occur above about T = 600 K, and around T = 1323 K, respectively. Our results were finally assessed with respect to similar vaporization studies carried out in neighboring ternary phase fields of the Na-U-O phase diagram. (C) 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).