Two new coordination polymers constructed from 5-sulfoisophthalic acid sodium salt (NaH(2)SIPA) and Co or Cu cations, [Co-3(SIPA)(2)(4,4 '-bpy)(4)(H2O)(6)]center dot 4H(2)O (1) and [Cu6O3(HSIPA)(3)(4,4 '-bpy)(6)(H2O)(3)]center dot 7H(2)O (2), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction (SXRD), powder X-ray diffraction (PXRD), IR spectroscopy, thermogravimetric analysis, UV-Vis spectroscopy, and elemental analysis. Compound 1 represents a twofold-interpenetrating 3-D framework based on Co, SIPA, and 4,4 '-bipyridine ligands with a qzd topology. Different from 1, compound 2 shows a 3-D self-penetrating framework based on Cu, HSIPA, and 4,4 '-bipyridine ligands. Furthermore, the photocatalytic performance in reduction of CO2 of 1 under visible light was investigated.