Two new metal coordination polymers [Zn(dpa)(bim)]n and [Ni(dpa)(bpp)]n, (H2dpa = 3,4′-Biphenyl-dicarboxylic acid, bim = Benzimidazole and bpp = 1,3-Di (4-pyridyl)-propane) have been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction. Single-crystal X-ray analyses reveal that the 3,4′-diphenic acids act as bridging ligands, exhibiting three coordination modes to link metal ions: μ2–η1: η1, μ1–η1: η0 and μ1–η1: η1. Compound 1 demonstrates a one-dimensional zigzag chain. There exists intermolecular hydrogen bonding interactions in compound 1 which lead to form supramolecular structure. Compound 2 is a two-dimensional (4,4) net, and further assembled twofold interpenetrating net. Furthermore, compound [Zn(dpa)(bim)]n shows intense photoluminescence at room temperature.