Two new phase of diammonium 5,5 '-bistetrazole-1,1 '-diolate (alpha- and beta-ABTOX) were prepared, and its structure were characterized by FT-IR spectroscopy and single X-ray diffraction. The thermal decomposition processes of alpha- and beta-ABTOX were studies by means of the DTA-TG and TG-MS technologies, the crystal morphology of alpha- and beta-ABTOX were studied by SEM technology. The results show thermal stability of alpha-ABTOX is better than beta-ABTOX, the crystal morphology of alpha- and beta-ABTOX are rhombus and square. Finally, front orbital energies and the molecular electronic potential (MEP) of alpha- and beta-ABTOX were studied using density functional theory (DFT) B3LYP/6-311G(d, p) basis set level.