The mixture of Catocene and fine AP after 175 °C heat treatment was washed by acetone and water, and the washing liquids of acetone and water were characterized by SP and microwave digestion‐ICP, and the solid products were characterized by XPS, XRD, SEM‐EDS. The results show that the oxidation of Catocene is a multi‐step reaction, and the final products are nano‐sized Fe2O3 and amorphous C. DTA‐TG test shows the productions can enhance the thermal decomposition of AP. Compared with the mixture of fine AP and Catocene, the mixture of fine AP and the final solid product of Catocene decomposition is insensitive to the impact. The effective constituents of Catocene catalysis for thermal decomposition of AP are nano‐sized Fe2O3 and amorphous C. Analyzing by synthesis, the final solid product may be an effective and safe catalyst for AP based propellant.