Recently, it has been reported that adding titanium into thermite composites can improve their combustion efficiency and lower their ignition temperature. However, the exact role of Ti reaction in such thermites is still unclear. Here, we put focus on in-depth understanding the reaction mechanism of Ti-based thermite by employing magnetron-sputtering technique to grow high purity and well-defined CuO/Ti nanolaminates. Nanolaminates feature a very well controlled interface and full contact between fuel and oxidizer compared to powered system showing random contact, which is crucial to identify and rationalize the different mechanisms taking place during initiation/propagation. This provides an ideal model-system to quantitatively describe the TiOx interfacial oxide growing using various characterization techniques including microscopy, thermal analysis, spectroscopy and X-ray diffractometric.