Two azide-bridged coordination polymers, [Cu(mptz)(N3)2] (1) and [Mn(mptz)(N3)2H2O] (2), (mptz = N-methyl-4-pyridinium tetrazolate), were synthesized and crystallographically and magnetically characterized. Compound 1 is a neutral 1D coordination polymer in which the CuII ions, which are in a square pyramidal surrounding, are linked by double end-on azide bridges in an alternating basal–basal and basal–apical fashion. Compound 2 exhibits a 3D MnII–azide coordination framework with the (10,3)-b net topology, in which the double end-on–azide-bridged dimanganese units are interlinked by single end-to-end azide bridges. The magnetic analyses indicated that 1 behaves magnetically as a quasi-dimer with an S = 1 ground state due to a strong ferromagnetic interaction through the basal–basal azide bridges and a very weak antiferromagnetic coupling through the basal–apical azide bridges. Compound 2 exhibits 3D antiferromagnetic behaviors with TN = 24.0 K, where the end-to-end and end-on azide bridges mediate the antiferromagnetic and ferromagnetic interactions, respectively.