In this paper, a semi-rigid dipyridyl-diamide ligand was selected as the organic linker to assemble with CoCl₂, and a new cobalt complex [Co(EDPB)Cl₂] (EDPB=(E)-4,4′-(ethene-1,2-diyl)bis(N-(pyridin-3-yl)benzamide)) was prepared under the solvothermal conditions. The structure and properties of the complex were tested by single crystal X-ray diffraction, powder X-ray diffraction, infrared spectra, thermogravimetric analysis, and solid-state UV-Vis diffuse reflectance spectra. It is found that the Co(II) atoms in the complex are tetracoordinated, which connect with EDPB ligands to form a 1D chain structure. The complex exhibits excellent absorption for visible light and highly heterogeneous catalytic activity for Cr(VI) reduction reaction with 97.9% of reduction rate in 60 min. The complex’s ability to be recycled for photocatalytic Cr(VI) reduction reaction was examined. Remarkably, it can be reused at least five times without any degradation in activity, showing its excellent cycling stability.