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In this study, a core-shell structure of MgAl-CuO nanothermite coated with ammonium perchlorate (KClO4@MgAl-CuO) has been successfully prepared by a solvent/non-solvent synthetic method, and its catalytic influence on the thermo-kinetic behavior of nitrated cellulose (NC)/diethylene glycol dinitrate (DEGDN) composite has been studied using differential scanning calorimetry (DSC) combined with three isoconversional kinetic models. Beforehand, scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR) findings showed that the prepared KClO4@MgAl-CuO particles were uniformly distributed within the NC/DEGDN matrix. Moreover, the obtained DSC thermograms indicated that the thermolysis of the developed NC/DEGDN composite was shifted to a lower temperature after the incorporation of the coated nanothermite. Additionally, a significant decrease in the activation energy (from approximately 136 to 94 kJ/mol) was also observed, demonstrating that the presence of the KClO4@MgAl-CuO nanothermite catalyzed the decomposition of NC/DEGDN propellant. Therefore, this study could serve as a reference for future research on the coated metastable intermolecular composites and their effects on double-base propellants. [ABSTRACT FROM AUTHOR]