3, 3′-Bis(N-hydroxy amidoxime)difurazanyl ether was synthesized from 3-cyano-4-nitrofurazan via etherification of nitro-group, addition, diazotisation and dioximation reaction with a total yield of 51.0%, and its structure and intermediates were characterized by IR, NMR and elemental analysis. The reaction conditions of dioximation were discussed and the optimum condition was obtained as follows: reaction temperature 20 ℃, n(DCFOF):n(NH₂OH·HCl):n(KOH)=1:4:4. Under alkaline conditions, DOFOF could be easily disproportionated to obtain 3, 3′-diamidoximinodifurazanyl ether. In addition, the reaction mechanism for disproportionation reaction of DOFOF was proposed.