An innovative synthesis of 5-((1H-tetrazol-5-yl)methyl)-4H-1,2,4-triazole-3,4-diamine (TMT) based on triazole and tetrazole frameworks bearing double amino groups was reported. It is worth mentioning that TMT is insensitive to impact and friction (IS > 40 J, FS > 360 N), thus enabling it to have an exceptional thermal decomposition behavior that is superior to RDX and TNT. Meanwhile, it also has relatively high energetic performance (Dv = 8.417 km/s). A series of energy-containing salts TMT-1-8 were also investigated for their potential applications. Except for TMT-4 and TMT-7, the remaining nitrogen-rich salts have initial decomposition temperatures above 200 °C. Furthermore, the salts with positive heat generation all have extraordinary gas production, especially for TMT-1 (Vo = 840.5 dm3/kg), TMT-2 (Vo = 803.9 dm3/kg), and TMT-7 (Vo = 844.3 dm3/kg). The low mechanical sensitivities of the TMT series were discovered, and a majority of them have impact sensitivities exceeding 40 J with friction sensitivities exceeding 360 N which are superior to TNT (IS = 15 J, FS = 353 N). The intermolecular and intramolecular interactions of the crystals TMT-1-3 were explored by Hirshfeld surfaces, 2D fingerprint plots, noncovalent interaction (NCI) analysis, and electrostatic potential surface analysis to understand the physicochemical property changes in relation to the structure. Consequently, this novel tri/tetrazole and polyamine system as a promising material provides the impetus for the development of gas generators and propellants.