The combustion process of energetic materials is a complex multi-stage process. Studying their thermal decomposition and combustion behavior is essential for developing precise combustion models. These models predict the thermal behavior of energetic materials accurately， crucial for their synthesis， production， transportation， storage， and application in modern weaponry and equipment. Third-generation materials have higher energy densities than traditional materials， demanding greater thermal stability. This review examines the thermal decomposition and combustion of third-generation energetic materials， including ionic energetic materials and covalent energetic materials. The research status of thermal properties and combustion reactions of typical third-generation energetic materials is expounded from three aspects: thermal decomposition map, thermal decomposition path and mechanism, and combustion performance research. The shortcomings of the current research are pointed out, and the research direction of the thermal behavior of the third-generation energetic materials is prospected. It is proposed to construct a multi-scale coupling research system : high-precision measurement of combustion parameters based on new test equipment, accurate diagnosis of combustion intermediates, and cross-scale modeling of quantum chemistry-machine learning-fluid mechanics to achieve full-chain analysis from free radical mechanism to macroscopic flame propagation.The contents consist of three aspects: thermal decomposition map， thermal decomposition path and mechanism， and combustion performance. The shortcomings of the current research are pointed out， and the research direction and development application prospect of the thermal behavior of the third-generation energetic materials are predicted.