In this Article, 11 silver complexes, namely, [Ag(L1)(2-Pyr)(H2O)] (1), Ag(L1)(2,3-Pyr) (2), [Ag2(L1)2(2Et,3Me-Pyr)2(H2O)] (3), [Ag(2,6-Pyr)](L1).1.5H2O (4), Ag(L1)(2,5-Pyr) (5), [Ag(H2O)2](L2).H2O (6), [Ag(L2)(2-Pyr)] (7), [Ag(L2)(2,3-Pyr)].1.5H2O (8), [Ag(L2)(2Et,3Me-Pyr)].2H2O (9), [Ag2(L2)(2,6-Pyr)(H2O)2](L2).H2O (10) and [Ag(L2)(2,5-Pyr)].H2O (11) (2-Pyr=2-methylpyrazine; 2,3-Pyr=2,3-dimethylpyrazine; 2Et,3Me-Pyr=2-ethyl-3-methylpyrazine; 2,6-Pyr=2,6-dimethylpyrazine; 2,5-Pyr=2,5-dimethylpyrazine; L1=p-aminobenzenesulfonate anion and L2=6-amino-1-naphthalenesulfonate anion), have been synthesized and characterized by elemental analyses, IR spectroscopy, and X-ray crystallography. In 1, 3, and 4, Ag(I) centers are linked by bridging pyrazine ligands to form one-dimensional chains, whereas compound 2 shows a double-chain structure through weak Ag-C interactions. The structure analyses show that both 5 and 11 form two-dimensional networks composed of 26-membered metallocycles. Unexpectedly, compounds 6 and 10 show discrete structures. In compound 7, silver(I) centers are bridged by sulfonate anions to form a polymeric helical structure, and the 2-Pyr molecule acts as a monodentate ligand. Compounds 8 and 9 show hinged chain structures containing 14-membered rings, and these chains interlace with each other to generate unique three-dimensional structures. These results indicate that the substituting groups and the substituting sites of pyrazine derivatives play an important role in the framework formation of silver complexes. Additionally, the luminescent properties of these compounds are also discussed.