AbstractA thermally stable and high nitrogen content energetic cation N,N'‐methylene‐bis(3,4,5‐triamino‐1,2,4‐triazolium) (MTAT, N = 69.38%, ΔHf = 1959.07 kJ/mol) has been used as a building block for preparing a new family of energetic salts. Compounds 1 and 4 were characterized by infrared and multinuclear NMR spectra. Structural confirmation of four salts (1–4) was supported by single‐crystal X‐ray diffraction. Theoretical calculations were performed to calculate the heats of formation and detonation performance using Gaussian 09 and EXPLO5 v6.05 programs, respectively. The impact and friction sensitivity of COMPOUNDS 1 and 2 were measured using BAM standards. Based on experimental and theoretical results, two energetic salts (1 and 3) featuring the novel cation framework MTAT exhibited favorable densities ranging from 1.751 to 1.809 g cm−3 at 298 K, excellent thermal stability (Td: 250–257 °C), acceptable detonation performance (D: 8001–8097 m s−1, P: 23.3–26.7 GPa), and good impact and friction sensitivity (IS: 18–40 J, FS: 240–360 N).