The reactions of AgNO3 with Na2L and Mg(HL)2 (H2L =5-sulfosalicylic acid) gave two luminescent coordination polymers: Ag2L(H2O) (1) and [Ag2(HL)2(H2O)3]H2O(2), respectively. 1 crystallizes in the monoclinic space group P2/n, with a = 7.489(2), b = 16.237(3), c = 8.222(2) Å , β= 92.90(3)°, V = 998.5(3) Å3, Z = 4. Compound 1 is the first silver carboxylate-sulfonate with an extended three-dimensional structure, a framework composed of four kinds of crystallographically unique silver atoms and organic species with three different functional groups, carboxylic, hydroxyl, and sulfonic, each coordinated to the silver atoms. 2 crystallizes in the triclinic space group Pī, with a = 8.307(2), b = 11.246(2), c = 12.590(3) Å, α = 112.68(3), β = 97.66(3), γ = 95.51(3)°, V = 1061.6(4) Å3, Z = 2. In 2, silver ions are bridged by sulfonate groups to form one-dimensional chains, and each chain is connected to the two neighboring chains through the coordination of the carbonyl oxygen atoms to the silver ions of the neighboring polymeric chain to form a two-dimensional network. The luminescent properties of the two compounds are also discussed.