The oxide shell of Al nanoparticles (Al NPs) prevents further reaction of Al/CuO nanothermites which reduces Al utilization efficiency and the performance of the nanothermites. However, the performance of Al/CuO nanothermites can be improved by adding ammonium perchlorate (AP). In this work, in order to confirm and explain the enhancement mechanism of AP on Al/CuO nanothermites, Al/CuO/NC and Al/CuO/NC/AP composites were prepared using the electrospray method. The composites were characterized by differential scanning calorimetry/thermogravimetric, x-ray diffraction, scanning electron microscope and transmission electron microscopy. Meanwhile, the ignition temperature and the time-resolved analysis of the rapid pyrolysis chemistry of the composites were tested using T-jump and time-of-flight mass spectrometry, respectively. The results show that Al NPs of Al/CuO/NC/AP composite are hollow compared to Al/CuO/NC composite after reaction. Al NPs and CuO NPs reduce the decomposition temperature and facilitate the rapid decomposition of the AP, and the decomposition products of the AP can destroy the oxidation layer of Al NPs. This result facilitates the further conduct of the thermite reaction. A mutually reinforcing relationship exists between the Al/CuO/NC composites and AP.