Three novel ferrocene-based hydrazone energetic transition-metal complexes denoted as M/E-FcDz-TMCs (M = Co (II), Fe (III), and Co(II)Fe(III)), were successfully prepared to improve the thermal decompositionof ammonium perchlorate (AP) and anti-migration performance of Fc-based catalysts. 1-hydrazinoethylene-ferrocene (E-FcDz) with unique electronic structure and energy bonds (C@N, NAN)as ligand reacted with transition metal Co, or Fe mono-metal nodes, and Co-Fe bimetal nodes, respectively. The chemical structure, crystalline texture, and morphology were confirmed, and the catalytic performancewas investigated. The thermal decomposition kinetics were estimated by applying Kissinger,FWO, and KAS methods. The results revealed that M/E-FcDz-TMCs had superior catalytic performancesfor AP decomposition compared to the traditional catalyst catocene due to their high electron transportcapacity. Especially, CoFe/E-FcDz-TMCs showed the best catalytic efficiency due to the hybridizationbetween Co (II) 3d and Fe (III) 3d orbitals in the structure led to electron redistribution, driving the optimalsynergistic catalytic effect of the bimetal Co-Fe nodes and E-FcDz, and further enhancing catalysis forAP. Moreover, AP/CoFe/E-FcDzTMCs showed the best combustion performance. In addition, the thermaldecomposition products of AP were explored by TG/FTIR, and the AP thermal decomposition processcould be explained by a possible mechanism following the principle of electron transfer theory.