Rationale: Ceria-based systems are of great interest because of their unique properties. Such systems may be used as anode materials for SOFCs or in oxygen sensors. The exploitation of these materials often requires high temperatures. In such conditions, the partial or complete evaporation of materials is possible. Therefore, knowledge of the values of partial pressures and thermodynamic properties is essential to predict and/or prevent possible consequences and accidents. Methods: Knudsen effusion mass spectrometry was used to determine partial pressures of vapor species over the SrO–CeO2 and CaO-CeO2 systems. Measurements of partial pressures were performed with a MS-1301 mass spectrometer. Vaporization was carried out using molybdenum or tungsten effusion cells. A theoretical study of gaseous strontium and calcium cerates was performed by several quantum chemical methods: density functional theory (DFT) M06, DFT PBE0, and MP2. Results: The minimum value of relative electron ionization cross-section for CeO2 was estimated. In the temperature range of 2218–2249 K above the SrO-CeO2 system and of 2128–2208 K above the CaO-CeO2 system, gaseous M, MO, MO, CeO2, O, O2 and MCeO3 (M = Sr, Ca) were found. Energetically favorable structures of gaseous SrCeO3 and CaCeO3 were found, and vibrational frequencies were evaluated in the “rigid rotor-harmonic oscillator” approximation. On the basis of the equilibrium constants of gaseous reaction MO + CeO2 = MCeO3, the standard formation enthalpy of gaseous SrCeO3 (−913 ± 26 kJ/mol) and of gaseous CaCeO3 (−917 ± 26 kJ/mol) at 298 K were determined. Conclusions: The estimated value of relative electron ionization cross-section for CeO2 is in agreement with the general rule applicable for dioxides. The stability of SrCeO3 and CaCeO3 gaseous species was confirmed by KEMS. Gas-phase reactions involving gaseous SrO (CaO) and CeO2 with gaseous SrCeO3(CaCeO3) were studied. Enthalpy of formation reaction of gaseous SrCeO3(CaCeO3) from gaseous SrO (CaO) were evaluated theoretically, and the obtained value is in agreement with the experimental one.