Perovskite-type LaFeO3 and alpha-Fe2O3 with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO3 and alpha-Fe2O3 for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO3 was much higher than that of alpha-Fe2O3 because of higher concentration of surface-adsorbed oxygen (O-ad) and hydroxyl of LaFeO3. The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition. (C) 2008 Elsevier B.V. All rights reserved.