Perovskite-type La0.8Sr0.2MnO3 was prepared by stearic acid gel combustion method. The obtained powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scaning electron micrograph (SEM) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic activity of La0.8Sr0.2MnO3 was investigated on thermal decomposition of octahydro-1,3,5,7-tctranitro-1,3,5,7-tetrazocine (HMX) by thermal gravity-differential scanning calorimetry (TG-DSC) techniques. The experimental results show that La0.8Sr0.2MnO3 is an effective catalyst for HMX thermal decomposition. The surface-adsorbed species such as H2O, OH- and adsorbed oxygen (O-ad) could result in an advance in the onset temperature of HMX thermal decomposition. The mixture system of Mn3+ and Mn4+ ions and lattice oxygen could play key roles for the increase of the decomposition heat of HMX because these exothermic reactions could be catalyzed by La0.8Sr0.2MnO3 between CO and NOx (from the thermal decomposition of HMX) and the oxidation reaction of CO. According to the previous researches and our results, perovskite-type La0.8Sr0.2MnO3 may be used as a novel catalyst or modifier for nitrate ester plasticized polyether (NEPE) propellant.