5-Nitro-3-trinitromethyl-1H-1, 2, 4-triazole(TNNT) and 5, 5′-bis(trinitromethyl)-3, 3′-azo-1H-1, 2, 4-triazole(BTNAT) were synthesized via condensation-cyclization, diazotization-substitution, oxidation-coupling and nitration reaction using aminoguanidinium hydrogen carbonate and malonic acid as raw materials, respectively.Their structures were characterized by IR spectrometry, NMR and elemental analyses.Their whole structure optimization and natural bond orbital(NBO) analysis were carried out at the B3LYP/6-31G(d, p) basis set level.Their decomposition temperature was measured by DSC.Results show that the decomposition temperature of TNNT and BTNAT under the conditions of 10 ℃·min^-1 and N₂ atmosphere is 135 ℃ and 146 ℃, respectively.