Differential thermal analysis, in air and argon, in concert with x-ray diffraction, was performed on 2- and 3-component mixtures of Al, B2O3, and TiO2, to foster an understanding of the reaction path involved in the TiB2-forming thermite reaction. In argon, aluminum reacted with B2O3 to form elemental boron, and reacted with TiO2 to form AlTi3. These two products reacted just after boron was made available at ∼1060 °C to form TiB2. Formation of Al18B4O33 by reaction between B2O3 reactant and Al2O3 product attenuated the yield of TiB2, but facilitated its formation by extraction of Al2O3 reaction barriers.