This study aims to compare the catalytic effects of three nano‐metal oxides (nMOs); Litharge (α‐PbO), Tenorite (CuO), and Hematite (α‐Fe2O3) on the thermal decomposition of an ammonium perchlorate based cross‐linked composite modified double base propellant (AP‐XLCMDBP). The three nMOs are synthesized via a chemical precipitation method and then characterized using XRD, FTIR, and SEM. Their effect on the thermal decomposition of AP‐XLCMDBP is studied using thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). The results indicate that Litharge has no significant effect on the thermal decomposition of AP‐XLCMDBP. However, both Tenorite and Hematite nanocatalysts accelerate the thermolysis process and enhance the total heat released from AP‐XLCMDBP. Moreover, compared to Tenorite, Hematite nanoparticles are found to be a more efficient catalyst, where their presence in AP‐XLCMDBP leads to a significant decrease in activation energies of the first and the second decomposition stages by 13.67 kJ/mol and 17.57 kJ/mol, respectively. An increase of the total decomposition heat by 153.73 J/g is also attained in the presence of Hematite, displaying its high catalytic action on the thermal decomposition of AP‐XLCMDBP.