Guanidinium azotetrazolate(GZT) was synthesized from 5-aminotetrazole (5-AT) by oxidation-reduction reaction and chemical combination reaction. The effects of reaction temperature,reaction time,molar ratio of reactants and NaOH concentration on the reaction were discussed. The proper technological conditions were identified as follows: based on 0.1 mol of 5-AT,NaOH concentration 1.5 mol?L^-1,n(5-AT)n(KMnO₄)=33,reaction temperature 80 ℃,reaction time 60 min. Under the known optimum conditions,scale-up test is made and the yield is more than 80%. The structure and characterization of the compound were characterized by element analysis,IR,¹H-NMR and TG-DTA technology.