A series of Cu(II) coordination polymers, [Cu(μ₂-L1)₃]PO₃F (1), [Cu₂(μ₂-L1)₄(μ₄-L1)](NO₃)₄·2H₂O (2), [Cu(μ₂-L1)₂(μ₂-X)]X·12H₂O (X = Cl, 3; Br, 4), [Cu₄(μ₂-OH)₂(μ₄-L1)₃(μ₂-L1)₂(H₂O)₂](CF₃SO₃)₆·10H₂O (5), [Cu₃(μ₂-OH)₂(μ₄-L1)(H₂O)₂(μ₃-SO₄)₂] (6), [Cu(μ₄-L1)(μ₂-SO₄)]·6H₂O (7), [Cu₂(μ₄-L2)₃]Cl·12H₂O (8) involving new bifunctional p-phenylene bridged bi(1,2,4-triazole) and mixed 1,2,4-triazole-tetrazolate based ligands (L1= 1,4-phenylene-4,4′-bi(1,2,4-triazole), HL2= 5-(4-[1,2,4]triazol-4-yl-phenyl)-1H-tetrazole) has been prepared under hydrothermal conditions and their structures have been established by means of X-ray diffraction. In crystal structures 1–8, the organic ligands, utilizing two neighboring nitrogen atoms (N1, N2 in triazole (trz) and N2, N3 in tetrazolate), behave either in μ₂ or in μ₂ + μ₄ manner binding the adjacent metal centers or Cu₃(μ₂-OH)₂ clusters into 1D columns (1, 3, 4), 2D zigzag layers (2) and 3D frameworks (5–8). The mutual coplanarity between uncoordinated trz moiety and p-phenylene spacer as well as its radial disposition around the “propeller-like” [Cu₂(η²-trz)₃] subunits is a crucial factor, which specifically mediates multiple π–π interactions through intercalation of the neighboring Cu(η²-trz)_n (n = 2,3) axles, and as a consequence, affording one-dimensional channels with trigonal (1, 2) or rhombic geometry (3, 4). Large rectangular channels have been realized in neutral [Cu(μ₄-L1)(μ₂-SO₄)]_n (7) and cationic [Cu₂(μ₄-L2)₃]_nⁿ⁺ (8) frameworks, in which the remaining void space is filled by water molecules and counter anions (Cl⁻).