The polymeric silver(I) thiolate complexes of [Ag-6(mu(3)-SC5H4N)(4)(mu(4)-SC5H4N)(2)](n) (1) and [Ag(mu(2)-SC5H4NH)Cl](n) (2) have been prepared from the controlled assembling reactions of silver chloride and 2-mercaptopyridine. X-ray diffraction analyses show that I has one-dimensional chain structure and 2 has three-dimensional network structure. The coordination geometry of each Ag(I) in 1 is a distorted tetrahedron of S3N, while that in 2 is a tetrahedron of S2Cl2. The sulfur atom of the thiolate ligand in I exhibits either mu(3) or mu(4) bridge linking three or four silver centers.