Two inorganic–organic hybrid complexes based on bi-capped Keggin-type cluster, {([CuII(2,2′-bpy)2]2[PMoVI8VV2VIV2O40(VIVO)2])[CuI(2,2′-bpy)]}∙2H2O (1) and {[CuII(2,2′-bpy)2]2[SiMoVI8.5MoV2.5VIVO40(VIVO)2]}[CuI0.5(2,2′-bpy)(H2O)0.5] (2) (bpy = bipyridine), had been hydrothermally synthesized and structurally characterized by elemental analysis, FT-IR, TGA, PXRD and X-ray single-crystal diffraction analysis. Compound1consists of a novel 1-D chain structure constructed from [CuI(2,2′-bpy)]+unit linking bi-supported POMs anion {[CuII(2,2′-bpy)2]2[PMoVI8VV2VIV2O40(VIVO)2]}−. Compound2is a bi-capped Keggin cluster bi-supported Cu-bpy complex. The main highlights of the two compounds are that Cu-bpy cations contain both CuIand CuIIcomplexes. Furthermore, the fluorescence properties, the catalytic properties, and the photocatalytic performance of compounds1and2have been assessed, and the results show that both compounds are active for styrene epoxidation and degradation and adsorption of Methylene blue (MB), Rhodamine B (RhB) and mixed aqueous solutions.