The first silver(I) complex of saccharinate (sac) with pyridine (py), [Ag(sac)(py)](n) has been synthesized and characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffractometry. The complex crystallizes in chiral, trigonal space group P3(1)21 (No. 152) with unit cell parameters of a = 11.2605(2) angstrom, c = 17.3300(4) angstrom, V = 1903.02(6) angstrom(3) and Z = 6. [Ag(sac)(py)](n) contains monomeric [Ag(sac)(py)] units linked into infinite helices by way of Ag...Ag interactions [d(Ag...Ag) = 2.909(2) and 2.985(1) angstrom]. The distorted square-planar environment of Ag is completed by an N-bonded sac [Ag-N = 2.084(2) angstrom] and a py molecule [Ag-N = 2.116(2) angstrom]. The N-sac-Ag-N-py angle is 173.85(10). The one-dimensional chains are crosslinked by C-(HO)-O-... interactions involving the carbonyl and sulfonyl O atoms of sac and aromatic-ring hydrogen atoms of both sac and py. The thermal stability of the title complex was investigated using thermogravimetry and differential thermal analysis in a static atmosphere of air. The first decomposition stage between 90 and 160 degrees C corresponds to removal of the py molecule in a single stage, while the degradation of the sac moiety occurs at two stages in the temperature range 370-515 degrees C, giving an end product of metallic Ag.