Among the materials that attract attention from the point of view of creating refractory products with increased heat resistance, one can single out materials based on compositions of the MgO – Al2O3 – TiO2 system. As a result of the thermodynamic analysis of the MgO – Al2O3 – TiO2 system, it was found that the partition of the system into elementary triangles will change in three temperature ranges: I – up to 1537 K, II – in the temperature range 1537 – 2076 K and above 2076 K. It has been established that up to a temperature of 2076 K there is a concentration range of spinel phases: magnesium aluminate spinel – quandylite. Above 1537 K, there is a concentration range: tialite – karroite, which meets the requirements for materials with high heat resistance. The elementary triangle TiO2 – Al2TiO5 – MgTi2O5 can be used to obtain heat–resistant materials based on Al2TiO5 stabilized by MgTi2O5. To obtain heat–resistant periclase–spinel materials, an elementary triangle Mg2TiO4 – MgAl2O4 – MgO is recommended, in which only compounds with a cubic crystal lattice are present. Thus, the division of the MgO – Al2O3 – TiO2 system into elementary triangles and the analysis of the geometrical–topological characteristics of the phases of the system made it possible to select in the system under study the regions of compositions that have optimal properties for obtaining materials with the specified optimal properties.