In this study, a new method was reported for the fabrication of the nanostructured CuO/Al thermite film on a Cu substrate. The CuO nanorod (NR) arrays grew vertically from the Cu surfaces by electrochemical anodization processes, followed by the deposition of an Al layer on the CuO NRs via magnetron sputtering to form a core/shell CuO/Al nanothermite film, whose component, structure and morphology were subsequently characterized. In addition, the energy-release characteristics of the obtained nanothermite film were investigated using thermal analyses and laser ignition tests. All evidence demonstrates that the obtained CuO/Al is of a uniform structure and has superb energy performance. Impressively, the resulting material is potentially useful in applications of functional energetic chips due to its easy integration with microelectromechanical systems (MEMS) technologies.