Diguanidinium 3, 3′-bis(nitramino)-4, 4′-azofurazanate (G₂DNAAF) was synthesized with total yield of 64% using 3, 4-diaminofurazan (DAF)as starting materials. The structure of G₂DNAAF was characterized by NMR, IR, elemental analysis and single crystal X-ray diffraction analysis. The thermal stability was analyzed by the differential scanning calorimetry (DSC) method. Furthermore, the enthalpy of formation and detonation parameters were calculated theoretically. Results show that the crystal of G₂DNAAF belongs to monoclinic system, space group P2(1)/n with a=5.226(2) Å, b=12.686(5) Å, c=11.944(5) Å, α=90°, β=92.896(7)°, γ=90°, V=790.8(5) ų, Z=2, D_c=1.698 g·cm^-3, μ= 0.148 mm^-1, F(000)=416. The decomposition temperature of G₂DNAAF is 259.0 ℃. The enthalpy of formation is 588.27 kJ·mol^-1, and the detonation velocity and detonation pressure are 7.839 km·s^-1 and 26.81 GPa, respectively.