The unique synthesis of 3-azido-5-amino-1,2,4-triazole (1) and a possible reaction process were described. The target compound 3,3 '-azo-5,5 '-diazido-1,2,4-triazole (2) was obtained by further coupling reaction of compound 1 with potassium permanganate. Compound 2 was well characterized by NMR spectra, IR spectroscopy, elemental analysis, differential scanning calorimetry (DSC), and single crystal X-ray diffraction. The sensitivities towards impact and friction of 2 were characterized by BAM Fallhammer and BAM Friction. Compound 2 exhibited good density (1.68 g cm(-3)), good thermal stability (193 degrees C), high heat of formation (1345.1 kJ mol(-1)/5.468 kJ g(-1)), excellent detonation performance (26.7 GPa, 8345 m s(-1) ) and acceptable sensitivity (IS=6 J, FS=72 N, EDS=0.224 J). Moreover, compound 2 was tested for its priming ability by detonating RDX. The result indicates that compound 2 could be used as a potential green metal-free primary explosive.