In the title complex, [Ag(NO(3))(C(9)H(7)N(3)OS)](n), η(1):η(1):η(1):μ(2)-bridging 2-(pyridin-4-ylsulfinyl)pyrimidine (pypmSO) ligands with opposite chiralities are alternately arranged to link the Ag(I) cations through two N atoms and one sulfinyl O atom of each ligand, leading to an extended zigzag coordination chain structure along the [ ̅201] direction. An FT-IR spectroscopic study shows a decreased stretching frequency for the η(1)-O-bonded S=O group compared with that of the free ligand. The parallel chains are arranged and interconnected via O(S=O)···π(pyridine/pyrimidine) and C-H(pyridine)···O(NO(3)(-)) interactions to furnish a layer almost parallel to the ac plane. Along the b axis, the layers are stacked and stabilized through anion(NO(3)(-))···π(pyrimidine) interactions to form a three-dimensional supramolecular framework. The ligand behaviour of the new diheterocyclic sulfoxide and the unconventional O(S=O)···π(pyridine/pyrimidine) and anion(NO(3)(-))...π(pyrimidine) interactions in the supramolecular assembly of the title complex are presented.