The triazole moiety with a high heat of formation and a high nitrogen content has been investigated for decades in combination with other nitrogen-rich heterocyclic rings in the field of energetic materials. A novel strategy for the construction of both thermally stable and mechanically insensitive energetic materials using a multi-aminotriazole system is now described. Using this methodology, two series of energetic materials were created on the basis of a duo of triazoles, 5-amino-3-(3,4-diamino-1,2,4-triazol-5-yl)-1H-1,2,4-triazole (TT), and a trio of triazoles, 4,5-di(3,4-diamino-1,2,4-triazol-5-yl)-2H-1,2,3-triazole (TTT). Their nitrogen-rich salts were also synthesized. Compound TT exhibits an excellent onset decomposition temperature (Td = 341 °C), which is superior to that of the conventional heat-resistant explosive hexanitrostilbene (HNS) (Td = 318 °C). The nitrogen-rich salt 4,5-di(3,4-diamino-1,2,4-triazol-5-yl)-2H-1,2,3-triazolium 3,4,5-trinitropyrazol-1-ide (TTT-1) exhibits both remarkable detonation properties and low sensitivities (Dv = 8715 m s-1; P = 32.6 GPa; IS > 40 J; FS > 360 N), which are superior to those of the traditional explosive LLM-105 (Dv = 8639 m s-1; P = 31.7 GPa; IS = 20 J; FS = 360 N). Therefore, this methodology of building a multi-aminotriazole system could effectively assist in the design of thermally stable and mechanically insensitive energetic materials in future exploration.