Four structurally diverse complexes, {[Pb(Hssal)(2,2′-bipy)](4,4′-bipy) 0.5 } n (1), [Pb 2 (Hssal) 2 (2,2′-bipy) 2 (4,4′-bipy)-(H 2 O) 2 ] (2), [Pb(Hssal)(phen)(4,4′-bipy) 0.5 ] n (3), and [Pb(Hssal)(2,2′-bipy)(bpe) 0.5 ] n (4), have been synthesized and characterized by elemental analyses, IR, thermogravimetric analyses, fluorescent spectra, and single-crystal X-ray analyses, where Hssal 2is doubly deprotonated 5-sulfosalicylate, 2,2′-bipy is 2,2′-bipyridine, phen is 1,10phenanthroline, 4,4′-bipy is 4,4′-bipyridine, and bpe is trans-1,2-bis(4-pyridyl)ethylene. The structure of complex 1 possesses a one-dimensional ladderlike chain with guest 4,4′-bipy molecules, while the molecular structure of complex 2 is a dimeric species with a coordinating 4,4′-bipy ligand. Complex 3 consists of a one-dimensional ladderlike chain with monodentate 4,4′-bipyridine but somewhat different from that of complex 1. Complex 4 is a two-dimensional layer structure. In 1−4, all 5-sulfosalicylates are doubly deprotonated, and all carboxylate groups of Hssal 2chelate to Pb II ions; however, the coordination modes of sulfonyl groups are different: syn−syn bridging in 1, noncoordinating in 2, syn-skew bridging in 3, and one-atom bridging in 4. The noncoordinating mode of sulfonate in Pb II complexes containing 5-sulfosalicylate is first reported in this presentation. The 4,4′-bipy ligands act as guest molecules in 1, dimeric linkers in 2, and monodentates in 3. The π−π stacking interactions can be observed in complexes 1−3, whereas there is no such interaction in complex 4. The coordination spheres of Pb II ions in 1−4 are controlled by three factors: the activity of a lone pair of electrons, weak Pb−O interactions, and π−π stacking interactions. The Pb II lone pair in 4 is inactive, whereas in 1−3, they are stereochemically active. The thermal stability and fluorescent property of complexes 1−4 are different from those of Pb II complexes only containing chelating ligands, [Pb(Hssal)(2,2′-bipy)(DMF)] n (5), and [Pb(Hssal)(2,2′-bipy)(H 2 O)] n (6), and [Pb(Hssal)-(phen)(DMF)] n (7).