The title compound, [Li(2)(C(5)H(4)NOS)(2)(C(2)H(6)O)](n), having two formula units in the asymmetric unit, forms infinite chains of Li(2)O(2) rhombi along b, consisting of four independent Li and O atoms. Metal binding to 2-thio-oxo-1,2-dihydro-pyridin-1-olate occurs in a bidentate fashion via O and S, and in a monodentate manner via the N-oxide O atom. π-π Inter-actions between polymeric chains are evident from centroid-to-centroid distances of pyridine-thione fragments of 3.461 (6)-3.607 (6) Å. The N-O and C-S bond lengths are distinctively different from those in hitherto investigated Ni(II), Zn(II) and (H(3)C)(2)Tl(III) complexes of 2-thio-oxo-1,2-dihydro-pyridin-1-olate, but correlate with those reported for 1-hydr-oxy- and 1-alkoxy-pyridine-2(1H)-thio-nes in the solid state.