AbstractPure, solvent‐free Zn(N3)2 was prepared by reaction of diethyl zinc and hydrazoic acid in aprotic solvents. The single‐crystal structure determination, along with the comprehensive characterization of α‐Zn(N3)2 and two metastable polymorphs, could be achieved for the first time. Since these data disagree in large parts with the known, previously reported values, all previous syntheses of Zn(N3)2, and for comparison Zn(N3)2⋅2.5 H2O and Zn(OH)N3 were reinvestigated, indicating that some of the earlier work has to be revised.