The synthesis of three heat-resistant explosive materials: 4,8-di(2,4,6-trinitrophenyl)difurazano[3,4-b:3′,4′-e]pyrazine (1), 4,8-di(2,4-dinitrophenyl)difurazano[3,4-b:3′,4′-e]pyrazine (2), 4-amino-8-(2,4,6-trinitrophenyl)difurazano[3,4-b:3′,4′-e]pyrazine (3),were reported and characterized by 1H NMR,13C NMR, IR as well as elemental analysis. X-ray crystallographic analysis confirmed the structure of 2, as well as displaying intermolecular hydrogen bonding. The thermal behaviors of these compounds were studied with differential scanning calorimetry (DSC) and thermal gravity-differential thermal gravity analysis (TG-DTG) methods. All the compounds showed good thermal stability with exothermic decomposition peaks in the range of 283 °C to 415 °C, on DSC. The sensitivities and calculated explosive performances were also reported for these energetic materials. All the results showed that polynitroaromatic substituted difurazano[3,4-b:3′,4′-e]pyrazines have the potential to be useful heat-resistant explosive materials.