A novel structure cobalt coordination polymer of {［Co(4,4′-bipy)(H2O)4］·(p-CH3C6H4SO3)2}n was prepared by solvothermal method with sodium p-toluenesulfonate as the main ligand and 4,4′-bipy as the auxiliary ligand. The cobalt coordination polymer was characterized by infrared spectroscopy, X-ray single crystal diffraction, thermogravimetric analysis and X-ray powder diffraction. The results show that {［Co(4,4′-bipy)(H2O)4］·(p-CH3C6H4SO3)2}n belongs to monoclinic system, P21/c space group; cell parameters of a=11.319 1(14) , b=8.062 6(11) , c=14.936(2) , α=90°, β=92.423(4)°, γ=90°, V=1 361.9(3) 3, Z=2. The central metal Co(Ⅱ) ion is a hexagonal octahedral structure with slightly distorted coordination. It forms a one-dimensional infinite chain through the bridging of N atoms in 4,4′-bipy. The interlayer is further expanded into a three-dimensional supramolecular structure through the hydrogen bonding between the coordination water molecule and p-methylbenzenesulfonic acid. The ［Co(4,4′-bipy)2(H2O)4］·(p-CH3C6H4SO3) structural unit in the cobalt coordination polymer was quantum chemically calculated by Gaussian 09 program, and the optimal configuration was obtained. The atomic charge distribution and the composition of the front occupied orbital well support the coordination environment of the crystal structure. Finally, the electrochemical impedance test shows that the resistance of the coordination polymer is small and the conductivity is good, which provides a certain theoretical basis for its electrochemical application.