The invention discloses a preparation method of zinc 5, 5'-azotetrazole, a green primary explosive. The method comprises: taking 5-aminotetrazole as the starting material, which is oxidized into sodium 5, 5'-azotetrazole by an alkaline oxidation method, then adopting pure water as the base solution, using a metering pump to control the feeding speed of a zinc acetate solution and a sodium 5, 5'-azotetrazole solution, and adding them dropwisely into the base solution for a combination reaction, then carrying out heat preservation, cooling, pumping filtration, washing, dehydration, and drying, thus obtaining a finished product of zinc 5, 5'-azotetrazole. The zinc 5, 5'-azotetrazole of the invention has the advantages of simple and safe synthesis method, low toxicity or no toxicity raw materials, low cost, no black residue after explosive decomposition, and small residue amount, generation of nitrogen as general gas product, no environmental pollution, as well as good explosion performance, thus being a green primary explosive.