Ammonium perchlorate (AP) as an oxidizer is widely employed in composite solid propellants (CSPs), and the thermal decomposition kinetics of AP can significantly affect the combustion behavior of CSPs. Therefore, the more apparent specific heat release at lower high-temperature decomposition (HTD) temperature of AP poses a challenge for the development of highly active catalysts.In this work, well-designed synergistic catalysts, cobalt nanoparticle embedded N-doped porous graphitized carbon (Co-NPs@NC), were obtained by straightforward high-temperature pyrolysis of the zeolite imidazolate framework-67 precursor under an argon atmosphere, among which Co-NPs@NC-800 exhibits excellent heat release ability and catalytic activity. The differential thermal analysis results indicated that the HTD temperature and apparent activation energy of AP with Co-NPs@NC-800, respectively, decreased by 133.0 °C and 86.3 kJ mol, while the heat release was increased by 5.4 times compared with that of pure AP. The excellent comprehensive properties of Co-NPs@NC-800 are attributed to the high catalytic activity of well-dispersed Co-NPs, the intrinsic adsorption capacity of Co-NPs for NH, and the synergistically enhanced effect of N-doped porous graphitized carbon to achieve good electrical conductivity and increase heat release, which facilitate its potential application as a high-efficiency catalyst for the thermocatalytic decomposition of AP.