Three new cluster-based Cu^II–azide coordination polymers, [Cu₈(N₃)₁₆(222-tet)₂]_n (1), [Cu₁₀(N₃)₂₀(dien)₂]_n (2), and [Cu₁₂(N₃)₂₄(Me₅dien)₂]_n (3) as well as a 1D polymer [Cu₂(N₃)₄(dien)]_n (4) were prepared by hydrothermal reactions of Cu^II ions with NaN₃ in the presence of various polyamines. Single-crystal X-ray diffraction studies reveal that 1 has a 1D chain structure based on an octanuclear cluster unit {Cu₈(N₃)₁₆(222-tet)₂}. Complexes 2 and 3 are 3D polymers and in both cases the azido anions display five different bridging modes (μ-1,1, μ-1,3, μ-1,1,1, μ-1,1,3,μ-1,1,1,3). Compound 4 is a 1D chain that represents the first example of a Cu^II–azide compound that contains cis-EE, double EO, and terminally bonded azido ligands. The magnetic susceptibility data, measured from 2 to 300 K, showed ferromagnetic couplings in 1, 2, and 4 and antiferromagnetic interaction in 3. The magnetic data of 1 and 4 were fitted with rough models, giving the exchange coupling constants J = 4.19 cm^–1 for 1 and J = 25.31 cm^–1 for 4.