4, 4′-Bis(chlorodinitromethyl)-3, 3′-azofurazan(BCNAF) was synthesized by using 4, 4′-dicyano-3, 3′-azofurazan as the starting material. The single crystal of target compound was cultivated by slow evaporation from methanol and its crystal structure was determined by X-ray single-crystal diffraction. Results show that it belongs to monoclinic system, space group P2₁/n, with cell parameters of a=7.5846(14) Å, b=8.4227(15) Å, c=12.324(2) Å, β=90.880(4)°, V=787.2(2) ų, Z=2, μ=0.494 mm^-1, F(000)=440. Crystal packing suggests that BCNAF is stabilized by highly symmetric structure, intermolecular π-π interaction as well as intramolecular halogen bonds. The thermal behavior of 4, 4′-bis(chlorodinitromethyl)-3, 3′-azofurazan was studied by using DSC-TG instrument, which showed that its decomposition peak was 142 ℃. Its calculated heats of formation is 816.5 kJ·mol^-1 by using Guassian09 and isodesmic reactions, which is higher than that of RDX. Its calculated detonation velocity (D) and detonation pressure (p) by EXPLO5 code are 8400 m·s^-1 and 30.8 GPa, respectively, which are close to those of RDX.