New C–N bonded energetic biheterocyclic compounds were synthesized using cine substitution of 1,3-dinitro-1,2,4-triazole with different energetic moieties. All the compounds were fully characterized by multinuclear NMR and infrared spectra, and elemental analyses. The structures of 4, 7, 9, and 11 were confirmed by single-crystal X-ray structure analyses. Their physicochemical properties, such as density, thermal stability and sensitivity towards impact and friction, were studied. All of the compounds have high thermal stability. The detonation properties were calculated with EXPLO5 V6.01 based on experimental densities and calculated heats of formation.