In this study, the structure formation of multicomponent composites based on Ti-C-Al, Ti-Al-C-Fe 2 O 3 and Ti-Al-C-TiO 2 powder mixtures under combine synthesis are considered. The features of Ti-C-Al, Ti-Al-C-Fe 2 O 3 and Ti-Al-C-TiO 2 composition synthesis that was accompanied by the formation of MAX phases and intermetallic compounds with different properties is studied theoretically and experimentally. An attempt is made to determine conditions and compositions of the starting powder mixtures for the powders composite materials with a complex multiphase structure. It is shown that during simultaneous process of wave combustion and metallothermy the inclusion and a matrix structure are formed with fundamentally different properties. Depending on the combination of the initial powder mixtures a metal matrix composite or ceramic composite can be formed. Metallothermal reactions initiated to obtain composites with oxide inclusions (in Ti-Al-C-Fe2O 3 and Ti-Al-C-TiO 2 powder systems) results in the occurrence of the non-equilibrium phases. These phases are not predicted from the preliminary thermodynamic evaluation but can be predicted based on thermokinetic models that include a set of possible chemical stages. It was shown that, in addition to intermetallic phases, the composition of the synthesis products includes the Ti 2 AlC phase which could be synthesized both in the combination with Fe 2 O 3 and using TiO 2 .