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A new one-dimensional double chain coordination polymer, [Na(cbsH)(H2O)3]n [cbsH = 4-carboxy-benzenesulfonic anion], has been synthesized by aqueous reaction, structurally described, as well as thermally characterized. It crystallizes in the triclinic system, space group P-1 with a = 5.645(4) A,B= 7.905(5) A, c = 13.043(8) A, a = 89.391(7)°, B = 80.637(7)°γ = 82.845(7)°, V= 569.8(6) A3, Z = 2, C7H11NaO8S, Mr = 278.21, Dc = 1.622 Kg/m3,F(000) = 288, R = 0.0260 and wR= 0.0697. The title compound consists of one-dimensional double chains. 4-carboxy-benzenesulfonic acid acts as a bridging bidentate ligand to link two sodium(I) ions to form a binuclear structure. Remarkably, the sodium(I) ion behaves as a metal bridge so that the binuclear structure units are connected to construct one-dimensional double chain polymer. Furthermore, a 3-D framework is assembled through intermolecular hydrogen bonds. Thermogravimetric analysis shows that this compound begins losing the free solvent molecules at 106 °C and decompounding completely at 580 °C.