This study reports on a new ternary thermite comprising of Al-TiB 2 /CuO multilayers, designed to take advantage of the high ignitability of titanium (Ti), high volumetric density of boron (B), and low melting point of aluminum (Al). Results demonstrate synergetic effects leading to an energetic layer outperforming single fuel counterparts, Al/CuO or TiB 2 /CuO, while being safe to handle. The additive TiB 2 not only lowers the ignition energy by 100%, but also enhances the burn rate by more than a factor of two compared to the single fuel samples (Al/CuO and TiB 2 /CuO). The thermite reaction sequences and synergy of Ti, B and Al oxidation, examined by thermo-analytical analyses coupled with X-ray spectroscopy and high-resolution electron energy loss spectroscopy, demonstrate the strong affinity of TiB 2 to oxygen that catalyzes CuO decomposition at temperatures as low as 380 °C; followed by a dual-step TiB 2 oxidation: first to TiO, and then to TiO 2 led by a reaction limiting step of oxidizer availability. Finally, Al undergoes oxidation via liquid boron oxide as well as gaseous oxygen. This study also underlines the crucial effect of the nanolayer morphology in the thin-film technology: when Al is sputter-deposited onto the TiB 2 layer, Al ions penetrate into the grain boundaries penalizing the TiB 2 reactivity. The results demonstrate the advantages of using TiB 2 fuel to improve the ignitability and combustion performance of Al based thermite and offers some means to finely tune their energetic properties.