Triaminoguanidinum azide (TAZ)is a promising ingredient for developing propellants with high specific impulse,low combustion temperature and low smoke used in missile or electrothermal chemical guns. The authors synthesized triaminoguanidinum nitrate (TAGN) and then transformed it into TAZ by reaction of sodium azide (NaN₃) with a kation-exchange resin,but it was inevitable to leave some solid impurities like unreacted NaN₃ and the by-product,NaNO₃,in the final product,and the yield of TAZ is only 23% based on TAGN. Therefore,this method is not beneficial to industrial production. In order to avoid the trouble above,the authors synthesized TAZ in non-aqueous medium by the reaction of free triaminoguanidinum (TAG) with the fresh acid of HN₃ formed by ion-exchange resin and NaN₃. The experimental results indicate that the reaction of sulfonate resin and NaN₃ in methanol can quantitatively produce HN₃ which is easy to be separated out and then react with pure TAG. This way,therefore,is promising to be used as an industrial procedure avoiding inorganic salts remained in the final TAZ product. The neutralization of TAG and HN₃ should be theoretically complete,but the yield of TAZ is only increase to 73.5% and 50% based on TAG and TAGN,respectively. The reason of incomplete neutralization should be further researched.