In comparison with the plasticizer only with azido， the one bearing multiple energetic groups not only generally has a higher density and oxygen balance， but also possesses more energy content. It endows the propellant with an increasing specific impulse and a better combustion performance， which has become a hot research topic in the field of the energetic material. However， it is an essentially important factor that how to precisely control the quantities and distributions of microscopic energetic groups in the plasticizer′s structure. To design and synthesize the plasticizer with high energy density， high thermal stability， high oxygen balance， insensitivity as well as low glass transition temperature， above-mentioned factor should be payed considerable attentions. This study reviews the previously reported azido plasticizers， containing nitro， nitrate， nitramine， difluoroamino and/or furazan group， from the design， synthesis and characterization of molecules to propellant applications since the late 1970s. Some drawbacks are sorted out in this paper. What′s more， several valuable suggestions to synthesize azido plasticizers with outstanding properties are presented here. It is essential worth noting that organic azido compounds with nitro and/or nitramine group are the most promising plasticizers used in propellant in the future， and the properties and synthetic difficulties of these materials are simultaneously taken into consideration. Finally， some guidance for researchers being engaged in the investigation of energetic plasticizers are provided.