4, 4'-Bis(dinitromethyl)-3, 3'-azofurazan (4) and potassium 4, 4'-bis(dinitromethyl)-3, 3'-azofurazanate (3) were synthesized from 4, 4'-dicyano-3, 3'-azofurazan through addition, diazotization and nitration with yield for each step reaction of 93.3%, 91.2%, 24.5% and 63.1%, respectively. In addition, a new furazan, 4, 4'-aminoxim-3, 3'-hydrazinefurazan (1), was obtained in the synthesis process of 4. This synthesis of 1 may proceed first with hydroxylamine addition of 4, 4'-dicyano-3, 3'-azofurazan followed by reduction of excessive hydroxylamine. The intermediates and product were analyzed by ¹H NMR, ¹³C NMR, IR and mass spectrum. The thermal behavior of 1, 3 and 4 were studied by DSC-TG method. The thermal behavior of 1 includes one dehydration endothermal stage and two obvious decomposition stages with mass loss of 5.1%, 53.5% and 36.3%, respectively. The peak temperature of each stage is 83.7℃, 241.1℃ and 336.2℃. The thermal behavior of 3 and 4 include only one obvious decomposition stage. The mass loss and the peak temperature are 86.6% and 258.1℃, 71.8%156.0℃, respectively.