Dihydroxylammonium 1, 1′-diolate-5, 5′-bistetrazole (TKX-50) was synthesized with a total yield of 63% via the reactions of oximation, chloration, azidation-cyclization and neutralization using glyoxal as starting material, and its structure was characterized by NMR, MS, IR. The effects of solvent, temperature and reaction time of azidation-cyclization reaction to synthesize an important intermediate 5, 5′-bistetrazole-1, 1′-diol dihydrate were optimized, as well as the neutralization reaction from 5, 5′-bistetrazole-1, 1′-diol dehydrate to TKX-50. Results show that the optimal conditions for azidation-cyclization are determined as: mixed solvent of acetone-water at 0 ℃ for 1.5 h and then extracted by diethyl ether, and the extract liquor directly into hydrogen chloride gas with the yield up to 88%. And for the neutralization reaction, the optimal conditions are as following: solvent of acetic ether at 50 ℃ for 2 h, with the yield of 94%.