The highly sensitive 5-azidotetrazolate anion was oxidized to its corresponding N-oxide by aqueous oxidation in a buffered oxone solution to the azidotetrazolate 2-oxide anion. After acidic extraction and neutralization with ammonia, the ammonium salt was isolated. Several energetic salts of this novel anion were prepared from the ammonium salt, and in all cases were found to be of lower sensitivity than the corresponding 5-azidotetrazolate salt while still being highly sensitive towards mechanical stimuli. Explosive performances (detonation velocity, detonation pressure) of applicable salts were also found to be higher than the non-N-oxide variants. Preparation of the free acid 2-hydroxy-5-azidotetrazole was achieved by protonation of the anion and identified by NMR spectroscopy, whereas the majority of the azidotetrazolate 2-oxide salts have unequivocal crystallographic proof.