To improve the combustion performance of ammonium perchlorate (AP), more high-performance combustion catalysts need to be developed. In this paper, five new types of energetic coordination complexes were prepared by combining 3aminofurazan-4-carboxylic acid (AFCA) with transition metals (Co, Ni, Fe, Cu, and Mn). The structures were determined by singlecrystal X-ray diffraction. Differential scanning calorimetry and thermogravimetric analysis were performed to characterize the thermal stability of the complexes. The five complexes exhibit superior energy properties to traditional explosive TNT. The thermal stability of the complexes was improved to a certain extent after binding to the metal. Catalytic experiments were performed by adding 10 wt % complexes to AP with differential thermal analysis instruments. Results indicate that the best catalyst is manganese as the metal center, which decreases the high-temperature decomposition (HTD) peak of AP by 133.3 °C and the activation energy (E) of AP by 102.2 kJ/mol and increases the mixture heat release by more than four times. Thermogravimetric analysis-Fourier transform infrared spectroscopy was applied to monitor the process of catalyzing AP, which indicates that the HTD of AP was advanced substantially. The combustion experimental results show that AP with complex 4 and complex 5 can burn vigorously. Overall, the furazan-based complex catalysts we synthesized have a good catalytic potential for solid propellant.