The paper presents the obtained results in the synthesis of thermoresistant pigments based on the Me²⁺→Co²⁺ substitution, where Me²⁺=Zn²⁺, Mg². The studied crystalline structures are: spinel – (ZnO, CoO, MgO)·Al₂O₃, olivine – 2(MgO,CoO)·SiO₂ and willemite – 2(ZnO, CoO)·SiO₂. The following synthesis methods were tested in parallel: the classical synthesis method – based on the annealing of mechanical mixtures of oxides or salts and the combustion synthesis method – using fuel mixtures. The behavior of the samples during the combustion synthesis was followed using thermal analysis. Phase and structural characterization of the samples was established by X-ray diffraction and IR spectrophotometry, and the colorimetric characterization was performed by VIS spectrophotometry.