A new series of silver complexes, [AgL], of the anionic forms of potentially bidentate N-2-pyridyl sulfonamide ligands [N-(3-methyl-2-pyridyl)-p-toluenenesulfonamide (HTs3mepy), N-(3-methyl-2-pyridyl)mesitylenesulfonamide (HMs3mepy), N-(4-methyl-2-pyridyl)-p-toluenesulfonamide (HTs4mepy), and N-(6-methyl-2-pyridyl)mesitylenesulfonamide (HMs6mepy)] have been prepared by an electrochemical procedure. In addition, heteroleptic complexes of composition [AgLL'] (L' = 1,10-phenanthroline and 2,2'-bipyridine) were obtained when the coligand L' was added to the electrolytic phase. The complexes were characterized by microanalysis, IR and H-1 NMR spectroscopy, and LSI mass spectrometry. In the cases of the compounds [Ag(Ts3mepy)](n) (1), [Ag-4(Ms3Mepy)(4)] (2a), [Ag(Ms3mepy)](n) (2b), [Ag-4(Ms6mepy)(4)] (3a), [Ag-2(Ms6mepy)(2)](n) (3b), [Ag-2(Ms3mepy)(2)(phen)(2)] (5), [Ag-2(Ms6mepy)(2)phen] (7), and [Ag-2(Ts4mepy)(2)(bipy)(2)] (8), characterization was also carried out by single-crystal X-ray diffraction. Compounds 1 and 2b present a polymer structure formed by an {AgN2} digonal core. Compounds 2a and 3a are tetranuclear and also have a distorted {AgN2} digonal core. Compound 3b is based on binuclear distorted {AgN2} digonal units joined by an intermolecular sulfonyl oxygen atom to produce a stairlike polymer structure. The heteroleptic complexes 5 and 8 are dimeric with a distorted {AgN4} tetrahedral geometry, while compound 7 shows two different geometries around the metal, distorted {AgN2} digonal and {AgN4} tetrahedral. The supramolecular structures of all species are organized by pi,pi-stacking, C-H...7, or C-H...O interactions.