The present study reports application of biphenyl-3,5-dicarboxylic acid (H2L) as a versatile building block for synthesis of d10 metal coordination polymers (CPs). Five Cd(II) and Zn(II)-containing CPs based on N,N-donor ancillary ligands, [Cd2(μ3-L)2(μ2-4,4′-tmbpy)(MeOH)]∞ (1), [Cd(μ2-L)(2,2′-bpy)(H2O)]∞·n(MeOH) (2), [Cd(μ2-L)(dipt)]∞ (3), [Cd(μ3-L)(phen)]∞·nH2O (4), and [Zn(μ2-L)(μ2-4,4′-tmbpy)]∞·nH2O (5) {4,4′-tmbpy = 4,4′-trimethylenedipyridine, 2,2′-bpy = 2,2′-bipyridine, dipt = 2,9-dimethyl-1,10-phenanthroline, phen = 1,10-phenanthroline} have been prepared under solvothermal conditions. 1–5 have been characterized by single crystal X-ray diffraction, elemental analysis, infrared (IR) spectra, and powder X-ray diffraction (PXRD). Complex 1 exhibits a three-dimensional (3-D) framework with a rare fsc-3,4-I41/amd topology. Complexes 2–4 show one-dimensional (1-D) structures. Complex 5 features a two-dimensional (2-D) layer structure with a sql topology. The structural and topological diversity of 1–5 are mainly attributed to the effect of the N,N-donor ancillary ligand. Solid-state luminescent properties and thermal stabilities of the obtained products have been investigated.