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This research work aimed to elaborate on a new modified double-base propellant containing nitrocellulose (NC), ammonium nitrate (AN), and diethylene glycol dinitrate (DEGDN). The developed AN/NC-DEGDN formulation was successfully obtained through a casting process and fully characterized in terms of its chemical structure, morphological features, and thermal behavior. Beforehand, theoretical calculation by the CEA-NASA program was applied to select the optimal composition of the formulation. Experimental findings demonstrated the homogenous dispersion of AN oxidizer in the NC-DEGDN matrix without alteration of their molecular structures. The catalytic influence of AN on the thermal decomposition behavior of NC-DEGDN film was also elucidated by thermal analyses. When AN was incorporated into the formulation, the decomposition peak temperatures for the different decomposition processes were shifted toward lower temperatures, while the total enthalpy of decomposition increased by around 1272.24 J/g. In addition, the kinetics of the thermal decomposition of the developed modified double base propellant were investigated using DSC results coupled with model kinetic approaches. It was found that the addition of AN decreases the activation energy of nitrate esters from 134.5 kJ/mol to 118.84 kJ/mol, providing evidence for its excellent catalytic effect. Overall, this investigation could serve as a reference for developing future generation of modified double-base propellants. Full article