The synthesis of ceramic materials based on europia-zirconia system and obtained by solid-state reaction in high-temperature vacuum press was investigated. Firstly, phase composition and calorimetric behavior of feedstock powders was investigated. The second part of the paper concerns the synthesis process of non-stoichiometric mixtures of feedstock powders prepared by four different methods of mixing. The influence of the homogenization method on the calorimetric behavior and phase composition of obtained sinters was studied. Finally, the influence of the additional high-temperature annealing was also investigated. From the obtained results, it can be concluded that the mixing procedure had a very strong influence on the morphology of obtained sinters. This is due to the structural inhomogeneity, as indicated by differences in phase composition. The synthesis process has a gradual character, and the obtaining of materials with different level of homogeneity allowed the determination of the order of subsequent intermediate phase formation.