The structures of two polymeric complexes of chromium(III) azide with pyridine, KCr(py)4(N3)4 (1), and RbCr(py)3(N3)4 (2), were determined by X-ray crystallography. Crystal data: 1, C20H20N16CrK, monoclinic, space group C2/c, a = 1611.2(5), b = 1050.6(3), c = 1609.0(5) pm, beta = 91.69(3)-degrees, Z = 4 and R(w) = 0.037 for 923 diffractometer data; 2, C15H15N15CrRb, monoclinic, space group P2(1)/n, a = 1311.9(3), b = 1139.0(4), c = 1523.3(4) pm, beta = 109.39(2)-degrees, Z = 4 and R(w) = 0.046 for 2336 data. The crystal structure of 1 contains six-coordinated chromium and potassium cations with two pyridine ligands and four mu(1,3) bridging azido groups forming a three-dimensional network structure. The chromium atoms are trans-coordinated by the pyridine ligands, whereas the potassium cations are cis-coordinated. The polymeric complex 2 features di-mu(1,1,3) azido bridged CrRbN2 rings, distorted octahedral chromium(III) coordination geometry, seven-coordinated rubidium, and di-mu(1,3) azido bridges which link the binuclear RbCr(pyridine)3(N3)2 moieties into infinite chains parallel to the b axis.