Abstract 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.