Nanolaminate Ti₃SiC₂-based material is prepared by self-propagating high-temperature synthesis (SHS) from elements, and the processes of its phase and structure formation is investigated. The Ti₃SiC₂ content in combustion products grows with an increase in the lifetime of the melt. The stratification observed at the level of the crystal structure results in the pronounced nanolaminate structure of Ti₃SiC₂ grains. The formation of the Ti₃SiC₂ phase occurs behind the combustion front with the interaction of stoichiometric TiC with the melt based on Ti-Si. Quantum-chemical calculations show that the formation of Ti-Si bonds is energetically preferable to Ti-C bond formation. A comparison of TiC and Ti₃SiC₂ crystal structures allow the assumption to be made that the laminate shape of Ti₃SiC₂ crystals is caused by the accumulation of structure discrepancies and hence by a lack of conjugation between the crystals.