A series of bistetrazole-based energetic salts bearing a nitrogen-rich fused ring were designed and synthesized. Among them, compounds 4-10 showed good detonation properties and excellent thermostability. By treating nitrogen-rich fused ring 3 with concentrated hydrochloric acid, a new type of Dimroth rearrangement was observed that afforded compound 12 efficiently. This new transformation herein constitutes a valuable addition to the Dimroth rearrangement.