A new lead complex, {[Pb(4-sb)(phen)](4,4′-bipy)0.5}n (1) (where 4-sb=4-sulfobenzoate dianion, phen=1,10-phenanthroline, 4,4′-bipy=4,4′-bipyridine), was synthesized and characterized by single-crystal X-ray, infrared, and thermogravimetric analyses and fluorescence studies. In this compound, the lead atom is hexacoordinated by two N atoms of one phen ligand and four O atoms from three 4-sb dianions. Each 4-sb serves as a bridging ligand, connecting adjacent PbII atoms into a centrosymmetric polymeric chain. Intermolecular π-π interactions and hydrogen bonds are observed in the complex, which stabilize the crystal packing and give rise to three-dimensional architecture.