Effects of Fe incorporation into Al–Ti–B4C reactants on the combustion behaviors, reaction mechanism, synthesized products, and possible natural convection of fluids were investigated. The incorporation of Fe significantly promotes the self-propagating reaction and decreases the reaction dependence on the B4C particle size. The prior reaction of Fe with B4C leads to the decomposition of B4C and formation of Fe2B and free carbon. On the other hand, the reaction of Fe with Ti and Al gives rise to the emergence of Fe–Ti and Fe–Ti–Al eutectic liquids. As a result, the diffusivity and reactivity of the dissociated carbon and boron atoms are greatly facilitated and the reaction is substantially promoted, yielding a desirable product of TiC, TiB2, and FeAl phases. Moreover, the incorporation of Fe may enhance free convection of the molten phase in the reaction zone and thus contribute to the combustion synthesis process.