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The copper oxide nanoparticles (nano‐CuO)/nitrocellulose (NC)/triethyleneglycol dinitrate (TEGDN)/diaminoglyoxime (DAG) nanocomposites were successfully prepared as a convenient propellants. The catalytic effect of nano‐CuO on the thermal behavior and the decomposition kinetics of the samples were precisely verified via thermogravimetry (TGA) and differential scanning calorimetry (DSC). The CuO nanoparticles significantly altered the thermal pattern of the studied energetic materials, e. g., the temperatures corresponded to the DSC peaks were changed by increasing the nano‐CuO amount. Moreover, the catalyst resulted in the decrement in the activation energy of the decomposition stage by ∼30–50 kJ mol−1 and also improved the thermal stability of TEGDN/NC/DAG composite. The thermokinetic and thermodynamic parameters of the energetic nanocomposites were explained by using the Kissinger and Starink differential methods and the integral methods of Coats Redfern and Flynn‐Wall‐Ozawa. The mechanism function and the kinetic equation of the main exothermal decomposition step for the parent composite was found to be different from that of the 1–3 % CuO‐contained nanocomposites.