In this article, a series of mixed-ligand Ag(I) coordination polymers, namely, Ag(L1)H2O (1), Ag-2(hmt)(2)(L1)(2) (2), [Ag(HL2)]H2O (3), [Ag(L2)(biim)][Ag(biim)] (4), [K-5(L-3)(2)][Ag(H2O)(2)] (5), [Ag-2(L3)(3-iso)][Ag(3-iso)]5H(2)O (6), [Ag-3(L3)(bipy)(3)(H2O)]6H(2)O (7), [Ag-3(L3)(biim)(3)]H2O (8), and [Ag-3(L3)(hmt)(2)(H2O)(3)]H2O (9) (where hmt = hexamethylenetetramine, bipy = 4,4'-bipyridine, biim = 1,1'-(1,4-butanediyl)-bis(imidazole), 3-iso = 3-methylisoquinoline, L1 = 2,5-dichloro-4-amino-benzenesulfonate anion, L2 = 2-nitroso-1-naphthol-4-sulfonate anion and L3 = 4-hydroxy5-nitro-1,3-benzenedisulfonate anion), have been synthesized by varying the anionic sulfonate-containing ligands and nitrogen-containing secondary ligands. Compounds 2 and 4 were synthesized through their parent compounds 1 and 3, respectively, while 6-9 were obtained by their parent compound 5. Ag(I) centers of 1 are linked by L1 anions to generate a 1D polymeric chain, while Ag(I) centers of 2 are bridged by brut ligands to form a 2D polymeric layer. In 3, Ag(I) centers are connected by L2 anions to yield a 1D double chain, whereas Ag(I) centers in 4 are joined by biim ligands and L2 anions, generating an unusual anionic chain and a cationic chain, respectively. In 5, Ag(I) centers are coordinated by water molecules, and K(I) cations are coordinated by L3 anions to form a pillared layered structure with inorganic layers and organic pillars. In 6, Ag(I) centers are coordinated by 3-iso ligands and L3 anions to generate a discrete molecular structure. In 7, bipy ligands bridge Ag(I) centers to give Ag bipy chains, which are further linked by L3 anions to produce a 2D polymeric layer. In 8, Ag(I) centers are bridged by biim ligands to generate a 1D polymeric chain. In 9, the brut ligands connect Ag(I) centers to give a binodal (3,4)-connected net with (6(3))(6(5).8)(2) topology. These results indicate that anionic sulfonate-containing ligands and the nitrogen-containing secondary ligands play important roles in the structural formation of the Ag(I) complexes. Additionally, the luminescent properties, elemental analyses and IR spectroscopy of these compounds were also studied.