With the development of aerospace science and technology, requirements for propellants are increasingly high. The thermal decomposition behavior of ammonium perchlorate (AP) directly influences the combustion performance of composite solid propellants. Catalysts play an important role in improving the thermal decomposition behavior of AP. In this study, three novel metal-organic frameworks (MOFs) were prepared using a straightforward method, namely Co[N(CN)2]2 (1; nitrogen content: 43.5%), Cu[N(CN)2]2 (2; nitrogen content: 43.0%), and Pb[N(CN)2]2 (3; nitrogen content: 24.8%). Their crystal structures were characterized and analyzed through single-crystal X-ray diffraction, forming interesting three-dimensional architectures. Moreover, derived composite catalysts under air (4, 6, and 8) or nitrogen (5, 7, and 9) atmosphere were generated by heating MOFs 1, 2, and 3-500 degrees C at a heating rate of 5 degrees C center dot min-1. The derived catalyst 4 exhibited the best performance. It reduced the decomposition peak temperature of AP by 81.9 degrees C, increased the heat release from 785 kJ center dot g-1 to 1232 kJ center dot g-1, and decreased the apparent activation energy (Ea) of AP from 223 kJ center dot mol-1 to 145 kJ center dot mol-1.