Bis-azoles and energetic ion derivatives are a new class of energetic materials, which have the features of high nitrogen content, high formation enthalpy, high detonation performance, and insensitivity.Recently, they have attracted more and more attention in the field of energetic materials due to their widely potential applications in the areas of new explosives, low signature propellant, gas generator, low smoke or smokeless fireworkss and so on.The progresses and properties of bis-1, 2, 4-triazoles, bistetrazoles, 5-(1, 2, 4-triazol-3-yl)tetrazoles and its energetic ion derivatives were reviewed.Nine kinds new type bis-azoles were designed in this paper and their performance is predicted by quantum chemistry methods.Researches on the law of various nitrogen-rich cations on sensitivity and detonation performance of bis-azoles and synthesis of new type bis-azoles with better performance are the keys of further work.