Four novel energetic ferrocene-based coordination derivatives, namely [M (FcHz)Á(NO 3 )] n (M = Co 2+ , Cu 2+ , Zn 2+ , and Fe 3+ ), were successfully prepared through a solvothermal method using 1,1 0 -bis(1-hydrazinoethylene) ferrocene (FcHz) with excellent electron transfer ability and energy bonds (C=N, N-N) as a ligand to coordinate with transition metals with high catalytic activity to promote the decomposition of ammonium perchlorate (AP). Their chemical structure, crystalline features, and morphology were comprehensively characterized, and their catalytic performance was analyzed. It is found that all [M (FcHz)Á(NO 3 )] n exhibited better catalytic performance for AP decomposition than that of traditional catalyst catocene because of the optimal synergistic effect between FcHz and transition metals. In addition, they had a large specific surface area, strong NH 3 absorption capacity, and high thermal property, which also could accelerate AP decomposition. [Co (FcHz)Á(NO 3 )] n was the best one, and AP with [Co (FcHz)Á(NO 3 )] n could decrease the high-temperature decomposition temperature and apparent activation energy of AP decomposition by 110 C and 75.82 kJ mol À1 , respectively, and increase heat release by 1066 J/g. The online thermogravimetric analyzer-coupled with a Fourier-transform infrared explored the AP decomposition products at different temperatures catalyzed by [Co (FcHz)Á(NO 3 )] n , and a possible catalytic mechanism was also proposed.The results indicate that [Co (FcHz)Á(NO 3 )] n with high efficiency, high energy, and high anti-migration has application prospects in AP-based solid propellants.