Abstract: A new 2-D inorganic–organic hybrid constructed from mixed-valence Cu(I/II) ions and mixed ligands, (H3sip=5-sulfoisophthalic acid, bipy=4,4′-bipyridine), has been synthesized and characterized by IR, TGA, XPS, EPR and single-crystal X-ray diffraction. Two different kinds of chains in the compound constructed from [CuO4] planar squares and [CuN2O] triangulars, respectively, further interconnect together to give rise to an interesting 2-D layer framework. The compound exhibits strong yellow emission at 445nm excited by 378nm in the solid state at room temperature. [Copyright &y& Elsevier]