(C6H14N2)[NH4(ClO4)3] is a newly developed porous hybrid inorganic-organic framework material with easy access and excellent detonation performances, however, its thermal properties is still unclear and severely hampered further applications. In this study, thermal behaviors and non-isothermal decomposi-tion reaction kinetics of (C6H14N2)[NH4(ClO4)3] were investigated systematically by the combination of differential scanning calorimetry (DSC) and simultaneous thermal analysis methods. In-situ FTIR spectroscopy technology was applied for investigation of the structure changes of (C6H14N2)[NH4(ClO4)3] and some selected referents for better understanding of interactions between different components during the heating process. Experiment results indicated that the novel molecular perovskite structure renders (C6H14N2)[NH4(ClO4)3] better thermal stability than most of currently used energetic materials. Under high temperatures, the stability of the cage skeleton constructed by NH4+and ClO4-ions determined the decomposition process rather than organic moiety confined in the skeleton. The simple synthetic method, good detonation performances and excellent thermal properties make (C6H14N2)[NH4(ClO4)3] an ideal candidate for the preparation of advanced explosives and propellants.