We herein describe a set of experiments used to study the effect of heating schedule on phase formation during the fabrication of Ti3SiC2-based materials from Ti–SiC powder mixtures by means of pressureless sintering. We found that combustion was initiated at a temperature of about 1330°C, which resulted in the formation of Ti-rich eutectic melt followed by crystallization of Ti3SiC2. It was shown that when preannealing was performed at 1150°C, no further combustive process could occur, and an intermediate, nonequilibrium phase composition, consisting of Ti5Si3Cx, TiC, and SiC remained until the end of the heat treatment. We herein discuss the mechanistic interpretation of this behavior.