Using a new ligand 1,6-bis(1,2,4-triazole-1-yl)hexane (L), one-dimensional coordination polymer Cu2(L)(CH3CO2)4n has been synthesized and characterized by elemental analysis, FTIR spectra and X-ray single crystal structural analysis. The title complex crystallizes in triclinic system with space group P1, a=0.722 5(7) nm, b=0.808 0(8) nm, c=1.173 1(11) nm, α=72.294(11)°, β=88.049(11)°, γ=66.294(11)°, V=0.594 2(10) nm3, Z=1, R1=0.037 0, wR2=0.098 3. The fundamental unit comprises two copper atoms (Cu(1), Cu(1A)), four μ2-bridged CH3CO2- and one ligand molecule. Cu(1) and Cu(1A) are both five-coordinated by four oxygen atoms from four μ2-CH3CO2- and one nitrogen atom from bridging ligand, forming a distorted square-pyramidal coordination configuration. Cu(1) and Cu(1A) are linked via four μ2-bridged CH3CO2- anions to form a paddle-wheel structural unit, which furthermore self-assemble into 1D chain via bridging ligands. CCDC: 603429.