Density functional theory (DFT) was used to study the molecular geometries, electronic structures, heats of formation in gas phase and in condensed phase, energetic properties, and thermal stabilities of triazole derivatives. The results show that the properties are associated with the different substituents and substitution positions in the parent ring. The symmetric structures and hyperconjugation systems both contribute to the thermal stabilities of the triazole derivatives. It is found that the group –N₃ is an effective structural unit forimproving the gas phase heat of formation. The calculated detonation properties indicate that –NO₂, –ONO₂, –N₃, –NF₂, and –CH(NO₂)₂ groups are very useful for enhancing the detonation velocities and detonation pressures. Thirteen compounds have better detonation properties than that of HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane). According to the quantitative data of energy and thermal stability for a nitrogen-rich high energetic compound, 20 out of 56 studied compounds may be considered as potential candidates with enhanced performance and reduced sensitivity.