Five new metalorganic complexes of the formula [Pb3L5(2,2-bipy)(2)(NO3)(H2O)] (n) 1, [Cd2L4(1,10-Phenanthroline)(2)] 2, [Mn2L4(1,10-Phenanthroline)(2)] 3, [Mn3L6(2,2-bipy)(2)] 4, and [PbL2(H2O)] (n) 5 [HL = 4-chlorophenyloxyacetic acid] have been synthesized and characterized by IR method, elemental analysis, X-ray powder diffraction (XRPD) analysis, fluorescence spectroscopy method, and single-crystal X-ray diffraction techniques. X-ray structure analysis reveals that complex 1 is 1D chain polymer, complex 5 is 2D network polymer, while complex 2, 3, and 4 are all 0D structure. The L ligand have many kinds of coordination mode, which make these complexes have different configuration. The weak CH center dot center dot center dot O and interactions are also very important, the mononuclear or multinuclear crystal units of these complexes can be packed through them. Moreover, all these complexes are exhibit fluorescence.