Using 3-azido-4-aminofurazan (AAF) as starting material, 3-azido-3′-nitrodifurazanyl ether (ANFO) was designed and synthesized for the first time via Caro′s acid oxidation, hydrolysis and intermolecular etherification sequence with a total yield of 32.7%, and the structures of ANFO and intermediates were characterized by ¹H NMR, ¹³C NMR, FT-IR, MS and elementary analysis. The oxidation method for 3-azido-4-nitrofurazan（ANF） was improved from hydrogen peroxide (50%), sulfuric acid and sodium tungstate as new oxidation system with a yield of 75.1%. The optimal conditions of oxidation and etherification were discussed, and the best conditions were obtained as follows: n(H₂O₂)∶n(H₂SO₄) is 1∶1.5 for oxidation system. The reaction temperature is at 30 ℃ for etherification system. The structure of ANFO was optimized by B3LYP/6-31G(d, p) method，the thermodynamic properties of ANFO at different temperatures were calculated on the basis of vibration analysis. The physicochemical properties and detonation performances of ANFO were studied by DSC measurement and the density functional theory (DFT) method. The calculated density, melting point, detonation velocity, detonation pressure, impact sensitivity(H₅₀) and heat of detonation are 1.85 g·cm^-3, 182.3 ℃(dec.), 8660 m·s^-1, 33.81 GPa, 35.2 cm and 6725 kJ·kg^-1, respectively.