In the present paper the structure and thermal properties of europium cerium oxides were investigated. The material for the research was obtained via solid state synthesis. The initial powders: ceria CeO2 and europia Eu2O3 were mixed in 1:1 mass ratio (non-stoichiometric proportion with the excess of CeO2) and milled. The sintering process was performed using high temperature vacuum press at 1350°C. Calorimetric analysis was conducted both for initial powders and milled mixture. The structure, phase composition and thermal diffusivity of obtained material were investigated in as-sintered condition. It was revealed that the obtained material was multi-phase. Non-stoichiometric phases including Ce0.5Eu0.5O1.75 with fluorite type structure and different lattice parameters were present. Thermal diffusivity decreased in the range from 25 to 900°C from 1.49 to 0.57 mm2/s and then increased to 0.70 mm2/s at 1400°C.