As a typical energetic substituent， N─NO₂ group exhibits high work capacity and is fundamental to the energy release of typical explosives such as RDX， HMX， and CL-20. Nitrogen-rich heterocyclic energetic compounds have garnered extensive research interest due to their high enthalpy of formation， high density， and environmental compatibility. However， the introduction of N─NO₂ is significant challenging due to the varying electrophilic reactivity of the NH sites in nitrogen-rich frameworks and the metastable structures of the energetic molecules. Therefore， summarizing the synthesis reactions and properties of various nitrogen-rich frameworks containing N─NO₂ is of great importance for the development of novel energetic materials with practical applications. This review categorizes nitrogen-rich energetic frameworks and summarizes the synthesis and properties of N─NO₂ in imidazole， pyrazole， triazole， and six-membered nitrogen-rich energetic heterocyclic compounds. The future development potential and research trend of nitrogen-rich energetic compounds with N─NO₂ nitration of heterocyclic NH groups are also prospected， so as to provide a valuable reference and guidance for the skeleton design， multi-functional group synergistic effect and synthesis of new N─NO₂ based energetic materials.