This work describes the first example to demonstrate the enhancement of performances of composite highly energetic materials by mean of employing standard CuO nano-powder as burning rate catalyst in comparison to micro-fillers. The solid composite propellants with CuO microparticles are less stable due to oversensitivity to pressure variations, but the nano-structured composite propellant yields high stable burning rates over a broad pressure range. In addition, the incorporation of CuO nanoparticles in the formulations of these energetic materials also improves their combustion and thermal properties, according to the characterization obtained by differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). These results indicate the excellent benefits found in using these nanoparticles as additive for solid rocket propulsion applications.