Five new coordination polymers, namely, [Ni2(L)2(4, 4′-bipy)3)]·H2O]n (1), [Ni2(L)2(O) (bpp)2]n (2), [Zn(L)(bib)0.5]n (3), [Zn(L)(PyBIm)]n (4), and [Zn3(L)2(OH)(im)]n (5) [H2L = benzophenone-2, 4′-dicarboxylic acid, 4, 4′-bipy = 4, 4′-bipyridine, bpp = 1, 3-bis(4-pyridyl)propane, PyBIm = 2-(4-pyridyl)benzimidazole, and im = imidazole] were synthesized under hydrothermal conditions. Structure determination revealed that compound 1 is a 3D network and exhibits a 4-connected metal-organic framework with (42.63.8) topology, whereas compounds 2, 3, 4, and 5 are two-dimensional layer structures. In compounds 2–4, dinuclear metal clusters are formed through carboxylic groups. In compound 5, trinuclear metal clusters are formed through μ3-OH and carboxylic groups. The carboxylic groups exhibit three coordination modes in compounds 1–5: monodentately, bidentate-chelating, and bis-monodentately. Furthermore, the luminescent properties for compounds 3, 4, and 5 were investigated.