This article presents a series of silver(I) coordination networks based upon nonchelating bidentate thioether ligands. Frameworks using AgOTs as the silver(I) starting material form two-dimensional frameworks and are quite stable as shown by differential scanning calorimetry/thermogravimetric analysis (DSC/TGA) data. The networks are sufficiently robust as to maintain the same layered motif when the basic skeleton of the ligand is sequentially derivatized with -OEt, OBu, and OHex groups. Crystal structures of the AgOTs complexes of the underivatized and bis(hexoxy) derivatives, compounds 5 and 8, respectively, are presented as well as powder X-ray diffraction (PXRD) data of the other complexes. For 5, C20H20S3O3Ag, crystal data are as follows: monoclinic, space group P2(1)/n, a = 11.8117(5) A, b = 7.8813(5) A, c = 22.3316(10) A, beta = 102.245(5) degrees, V = 2031.6(2) A(3), Z = 4. For 8, C30H44S3O6Ag, crystal data are as follows: triclinic, space group Ponebar a = 8.445(4) A, b = 10.855(5) A, c = 19.308(9) A, alpha = 84.53(1) degrees, beta = 78.76(1) degrees, gamma = 68.43(1) degrees V = 1613.9(13) A(3), Z = 2. Changing the silver(I) starting material to AgPF6 results in a shift to a one-dimensional structure, 9, as shown by X-ray crystallography and in highly compromised stability. For 9, C14H16S2N2PF6Ag, crystal data are as follows: monoclinic, space group P2/n, a = 11.9658(11) A, b = 3.9056(4) A, c = 19.6400(18) A, beta = 92.87(1) degrees, V = 916.70(15) A(3), Z = 4.