The azo functionality is not only a bridging block， but also can generally increase the density and heat of formation of energetic nitrogen-rich heterocycles. Therefore， building new energetic materials through the bridging method has gradually become a research hotspot in this field. This article reviewed synthesis method， physical and chemical properties and detonation properties of azo-bridged nitrogen-rich heterocycles focusing on azoles and azines from C—NH₂ and N—NH₂ oxidative couplings. This review will provide some references for the research and development of new azo-bridged nitrogen-rich heterocycles.