The reaction of diazotetrazole with nitroacetonitrile led to the isolation of the simple 1,2,4-triazine-based energetic 3-azido-5-amino-6-nitro-1,2,4-triazine. It and related compounds were chemically characterized by NMR, IR, and single-crystal X-ray crystallography. Their energetic sensitivities (impact, friction) were experimentally determined and energetic performances calculated. The ability of 3-azido-5-amino-6-nitro-1,2,4-triazine to form N-oxides was also studied.