Large particle size and low specific surface area are two major factors of restricting metal oxides as combustion catalyst with high performance. The construction of three-dimensional (3D) heterojunction materials with synergistic effect is conducive to enhancing the catalytic activity. In this work, LaFeO3 were prepared by a facile solvo-thermal method and post-heat treament. However, the LaFeO3 with a large particle size shows poor specific surface area, resulting in a low catalytic activity. In order to improve its catalytic activity, a 3D core/shell heterostructured LaFeO3@MnO2 composite was constructed by coupling LaFeO3 with MnO2. The core-shell structured LaFeO3@MnO2 provides a larger specific surface area and high catalytic effect on the thermal decomposition of ammonium perchlorate (AP) with a reduced decomposition temperature from 403.73 degrees C to 281.38 degrees C, an enhanced energy release from 649.6 J.g(-1) to 966.5 J.g(-1), and a decreased apparent activation energy from 139.05 kJ.mol(-1) to 110.88 kJ.mol(-1). Additionally, LaFeO3@MnO2 also shows efficient catalytic effects on the thermal decomposition of hexanitrohexaazaisowurzitane (CL-20) and cyclotetramethylenetetranitramine (HMX). (C) 2020 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.