Due to the chemically unstable nature of uranium dioxide its vapor composition at very high temperatures is, presently, not sufficiently studied though more experimental knowledge is needed for risk assessment of nuclear reactors. We used laser vaporization coupled to mass spectrometry of the produced vapor to study urania vapor composition at temperatures in the vicinity of its melting point and higher. The very good agreement between measured melting and freezing temperatures and between partial pressures measured on the temperature increase and decrease indicated that the change in stoichiometry during laser heating was very limited. The evolutions with temperature (in the range 2800–3400 K) of the partial pressures of the main vapor species (UO2, UO3, and UO2 + ) were compared with theoretically predicted evolutions for equilibrium noncongruent gas-liquid and gas-solid phase coexistences and showed very good agreement. The measured main relative partial pressure ratios around 3300 K all agree with calculated values for total equilibrium between condensed and vapor phases. It is the first time the three main partial pressure ratios above stoichiometric liquid urania have been measured at the same temperature under conditions close to equilibrium noncongruent gas-liquid phase coexistence