Zinc azide · 3-methylpyridine is formed by reaction of 3-methylpyridine with zinc azide in water/methanol solution. The structure of the title compound has been determined from three-dimensional X-ray data and refined by full-matrix least-squares to a final R value of 0.050 for 1276 MoKα reflections at 98 K. The crystals are monoclinic, space group P21/c, Z = 4, with a. = 6.071(4), b = 21.180(11), c = 7.615(5) Å and β = 99.53(4)°. Each zinc atom is surrounded by five nitrogen atoms (four from azide groups and one from the pyridine adduct) in a distorted trigonal bipyramidal fashion. The ZnN5-polyhedra share common edges to form chains along the crystallographic a-axis.