Twelve energetic nitrogen-rich salts based on 3-azido-N-nitro-1H-1,2,4-triazol-5-amine were prepared and fully characterized by 1H, 13C NMR, and IR spectroscopy, differential scanning calorimetry (DSC), and elemental analysis. The crystal structures of the neutral compound 3-azido-N-nitro-1H-1,2,4-triazole-5-amine (1) and its triaminoguanidinium salt (13) were determined by single-crystal X-ray diffraction. The density of 1 and its twelve salts ranged from 1.57 to 1.79 g cm−3, and the heat of formation was calculated with the Gaussian 03 suite of programs. Compounds 1–13 exhibit promising detonation performances (pressure: 25.3–39.3 GPa; velocity: 8159–9409 ms−1; EXPLO 5.05). Impact sensitivities were also determined by hammer tests and resulted ranging from 2.5 J (very sensitive) to >40 J (insensitive).