This article represents a systematical examination of the structures of silver(I) sulfonates incorporating neutral ligands. To survey the influence of the properties of neutral ligands on the structures of silver(I) sulfonates, three kinds of sulfonate anions (L1= 1-naphthalenesulfonate, L2 =p-toluenesulfonate,and L3 = 1, 3, 6, 8-pyrenetetrasulfonate) and three kinds of neutral ligands (pyrazine, Pyr, a divergent bidentate ligand; hexamethylenetetramine, hmt, a divergent tetradentate ligand; and β-picoline, Pic, a monodentate ligand) were selected for study, and five novel silver (I) sulfonates containing neutral ligands have been synthesized: [Ag(L1)- (Pyr)] •H2O(1), Ag(L2)(Pyr) (2), Ag4 (L3) (Pyr)4 (H2O)2 (3), [Ag(L1)(hmt)] •H2O(4), and Ag(L1)(Pic)2 (5). The crystal structures have been determined by single-crystal X-ray diffraction,and these compounds show a variety of structures with different dimensionalities. Moreover, the luminescent properties of compounds 2, 4, and 5 are also discussed.