A series of new energetic compounds with different energetic groups (such as amino, nitroamino, gem-dinitro, and trinitromethane) based on bis-5,6 fused triazole-triazine have been readily synthesized and fully chemically characterized. Four of them (6, 7, 8 and 11) were further confirmed by single-crystal X-ray diffraction. The physical and energetic properties of all the prepared energetic compounds, including density, heat of formation (HOF), thermal stability, calculated detonation velocities, and detonation pressures, were investigated. The densities of compounds 6–9, 11 are located in the range of 1.69–1.85 g cm−3, while the detonation velocities and detonation pressures exhibt a superior performance in the range of 7560-8988 m s−1 and 21.0-35.6 GPa respectively. Benefiting from the high density and hydrogen bonds, compound 9 show highest detonation performance and relatively low sensitivities (IS=10 J, FS=128 N). In addition, the effects of the different energetic groups on the sensitivity, density, and decomposition temperature are discussed based on experimental results and the crystal structures.