Fe2O3Co3O4 composites were fabricated based on hydrothermal process and subsequent annealing treatment and characterized by several techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Photoluminescence (PL) and electrochemical impedance spectroscopy (EIS). The catalytic performances of Fe2O3Co3O4 composites in the thermal decomposition of ammonium perchlorate (AP) were investigated using thermogravimetric and differential thermal analyses (TG-DTA) analysis. The results revealed that Fe2O3Co3O4 composites showed superior catalytic behaviors for AP pyrolysis compared to pure Fe2O3, Co3O4 as well as CoFe2O4 samples, ascribed to the synergistic interactions between Co3O4 and Fe2O3 enhancing electron transfer capability. Especially, the as-obtained Fe2O3@Co3O4 displayed the best catalytic efficiency with the high temperature decomposition (HTD) of AP reducing by 156 °C in the case of 2 wt% addition. Online TG-FTIR was used to detect the decomposed products of AP, and the catalytic mechanism was discussed.