Abstract: Two novel metal-organic complexes Co(Hbmp)₂(H₂O)·TFBDC(1), Co(Hbmp)(TDC)(H₂O)_n(2) Hbmp=2-(2-benzimidazolyl)-6-methylpyridine, H₂TFBDC=tetrafluoroterephthalic acid, H₂TDC=2,5-thiophene dicarboxylic acid have been hydrothermally synthesized. Their structures were characterized by X-ray single crystal diffraction, X-ray powder diffraction, elemental analysis and infrared spectroscopy. The results showed that the crystal system of complex 1 is rhombohedral, Fddd space group, with the central ion Co(Ⅱ) in a triangular bipyramidal configuration and cell parameters of a=1.47278(11) nm, b=2.9178(3) nm and c=3.0274(2) nm. The crystal system of complex 2 is monoclinic, C2/c space group, with the central ion Co(Ⅱ) in an octahedral configuration and cellparameters of a=1.77753(17) nm, b=1.84660(17) nm, c=1.33365(12) nm. The zero-dimensional structure of complex 1 forms a three-dimensional supramolecular network through the rich hydrogen bonding forces of C—H···O, C—H···F, N—H···O, O—H···O. Complex 2 is a one-dimensional chain structure of the neighbouring metal Co(Ⅱ) using the two coordination modes of carboxylic acids, which is also expanded into a three-dimensional supramolecular mesh structure with the help of abundant hydrogen bonding forces. Using UV diffuse reflectance spectroscopy, an E_g value of 2.65 eV for 1 and 2.85 eV for 2 were obtained, demonstrating that both complexes are potential semiconductor materials. The magnetic property of the two complexes was also investigated at 2−300 K with an external magnetic field of 1000 Oe and magnetic susceptibility data were rationallyfitted with the Curie-Weiss Law at 2−300 K with θ=−5.13 K and −5.84 K, respectively, demonstrating the existence of antiferromagnetic interactions between the two complexes.