Three Cu-based coordination polymers (CPs), including [CuII (𝑁 -𝜂1 -NCS)2 (O-𝜂1 -DMF)2 (𝜇2 -3,3’-bptz)]𝑛 (1), [CuI (1,3-𝜇2-NCS)(𝜇2-3,3’-bptz)]𝑛 (2) and [(CuI (1,3-μ2- NCS))(𝜇2-4,4’-bptz)]𝑛 (3) (DMF = 𝑁, 𝑁-dimethyl formamide, 3,3’-bptz = 3,6-bis(3-pyridyl)tetrazine and 4,4’-bptz = 3,6-bis(4-pyridyl)tetrazine) have been successfully constructed by solution diffusion reactions by using Cu(NO3)2 ·3H2O or CuNCS and KNCS with 3,3’-bptz / 4,4’-bptz ligands, respectively. The resulting crystalline materials have been characterized by the single-crystal X-ray diffraction analyses, elemental analyses, FT-IR spectra, thermogravimetric analyses and powder X-ray diffraction (PXRD). Single crystal X-ray analyses revealed that CP 1 is organized in one-dimensional (1D) chain in which the Cu(II) ions are coordinated by 𝜂1 -NCS− anions and 𝜂1-DMF molecules, and linked by 𝜇2-3,3’-bptz bridging ligands. CPs ,2 and 3 are structural isomers. CP 2 exhibits two-dimensional (2D) (4,4)-plane-like network in which Cu(I) ions are linked by 𝜇2-NCS − and 𝜇2-3,3’-bptz ligands. In CP 3, Cu(I) ions are connected by 𝜇2 -NCS − and 𝜇2-4,4’-bptz ligands to form 2D saw-tooth wavy network. In addition, the photoluminescence properties of CPs 1-3 were also investigated in the solid state at room temperature.