（C₆H₁₄N₂）［Na（ClO₄）₃］ is a representative of energetic perovskite compounds. It is necessary to clarify the corresponding thermal decomposition behavior， thermal decomposition mechanism and sensitivity characteristics in order to promote the application in formulations. Thermal decomposition parameters， including heat release amount and decomposition temperatures， were obtained by simultaneous differential scanning calorimetric and thermogravimetric analyses methods. The relevant decomposition mechanism was analyzed by kinetic simulation calculations. The decomposition products and decomposition processes of （C₆H₁₄N₂）［Na（ClO₄）₃］ were explored by DSC/TG-FTIR-MS coupled technique combined with in-situ infrared technology. The parameters of thermal sensitivity， friction sensitivity and impact sensitivity were obtained by national military standard methods. The results show that the heat of decomposition of （C₆H₁₄N₂）［Na（ClO₄）₃］ is 4227 J·g^-1 at the heating rate of 10 ℃·min^-1 and the decomposition temperature reaches 345 ℃， which is higher than that of most active energetic materials， including Hexogen （RDX）， ogen （HMX） and hexanitrohexaazoisowuzane （CL-20）， indicating an outstanding thermal stability. The decomposition products analysis shows that the cubic cage-like skeleton effectively stabilizes the internal organic molecule， resulting in the high thermal stability of （C₆H₁₄N₂）［Na（ClO₄）₃］. In addition， the outgassing amount of （C₆H₁₄N₂）［Na（ClO₄）₃］ heated at 100 ℃ for 48 h is about 0.04 mL·g^-1， and the impact sensitivity and mechanical sensitivity are 32% and 80%， respectively， which are better than RDX and HMX.