The combustion process of energetic materials （EMs） is a complex multi-stage process. By studying their thermal decomposition and combustion reactions， establishing precise combustion reaction kinetics models enables effective prediction of the thermal behavior of EMs， which is of significant importance for their synthesis， production， transportation， storage， and practical application in modern weaponry and equipment. Compared to traditional EMs， third-generation EMs exhibit higher energy density， which imposes more stringent requirements on their thermal stability. This review summarizes recent advances in thermal properties and combustion research of third-generation EMs， including both ionic and covalent types. The current research status on thermal properties and combustion reactions of typical third-generation EMs is expounded from three perspectives： thermal decomposition profiles， decomposition pathways/mechanism， and combustion performance. It identifies the shortcomings of the current research and proposes the research direction of the thermal behavior of the third-generation energetic materials. It is proposed to construct a multi-scale coupled research system： high-precision measurement of combustion parameters via novel experimental apparatus， accurate diagnosis of combustion intermediates， and cross-scale modeling combining quantum chemistry-machine learning-fluid mechanics to achieve full-chain analysis from free-radical mechanisms to macroscopic flame propagation.