Self-assembly of silver(I) salts and three ortho-hydroxyl and carboxyl groups decorated arenesulfonic acids affords the formation of nine silver(I)-sulfonates, (NH4)center dot[Ag(HL1)(NH3)(H2O)] (1), {(NH4)center dot[Ag-3(HL1)(2)(NH3)(H2O)]}(n) (2), [Ag-2(HL1)(H2O)(2)](n) (3), [Ag-2(HL2)(NH3)(2)]center dot H2O (4), [Ag(H(2)L2)(H2O)](n) (5), [Ag-2(HL2)](n) (6), [Ag-3(L3)(NH3)(3)](n) (7), [Ag-2(HL3)](n) (8), and [Ag-6(L3)(2)(H2O)(3)](n) (9) (H(3)L1 = 2-hydroxyl-3-carboxyl-S-bromobenzenesulfonic acid, H(3)L2 = 2-hydroxyl-4-carboxylbenzenesulfonic acid, H(3)L3 = 2-hydroxyl-5-carboxylbenzenesulfonic acid), which are characterized by elemental analysis, IR, TGA, PL, and single-crystal X-ray diffraction. Complex 1 is 3-D supramolecular network extended by [Ag(HL1)(NH3)(H2O)](-) anions and NH4+ cations. Complex 2 exhibits 3-D host-guest framework which encapsulates ammonium cations as guests. Complex 3 presents 2-D layer structure constructed from 1-D tape of sulfonate-bridged Ag1 dimers linked by [(Ag2)(2)(COO)(2)] binuclear units Complex 4 exhibits 3-D hydrogen-bonding host-guest network which encapsulates water molecules as guests. Complex 5 shows 3-D hybrid framework constructed from organic linker bridged 1-D Ag-O-S chains while complex 6 is 3-D pillared layered framework with the inorganic substructure constructing from the Ag2 polyhedral chains interlinked by Ag1 dimers and sulfonate tetrahedra. The hybrid 3-D framework of complex 7 is formed by L3(-) trianions bridging short trisilver(I) sticks and silver(I) chains. Complex 8 also presents 3-D pillared layered framework, and the inorganic layer substructure is formed by the sulfonate tetrahedrons bridging [(Ag1O(4))(2)(Ag2O(5))(2)](infinity) motifs. Complex 9 represents the first silver-based metal-polyhedral framework containing four kinds of coordination spheres with low coordination numbers. The structural diversities and evolutions can be attributed to the synthetic methods, different ligands and coordination modes of the three functional groups, that is, sulfonate, hydroxyl and carboxyl groups. The luminescent properties of the nine complexes have also been investigated at room temperature, especially, complex 1 presents excellent blue luminescence and can sensitize Tb(III) ion to exhibit characteristic green emission.