Three new hybrid compounds based on similar molybdenum-vanadium clusters and several types of copper complexes, [Cu(enMe)2][Cu(enMe)2(H2O)]2[HPMo9.25V4.75O42] (1), [Cu(2,2′-bpy)2]3[Cu(phen)2]2[PMo10V4O42] (2) and [Cu(im)2]{[Cu(2,2′-bpy)2]2[PMo8V6O42]}·3H2O (3) (enMe = 1,2-propanediamine, im = imidazole, bpy = bipyridine, phen = 1,10-phenanthroline), have been synthesized and characterized by IR, UV–Vis spectrum, powder XRD, photoluminescence analysis, elemental analysis and X-ray diffraction analysis. Single crystal X-ray analysis reveals that compound 1 exhibits a 3-D supramolecular structure constructed from bi-capped Keggin molybdenum-vanadium polyoxoanions and copper-propanediamine complexes. Both compound 2 and 3 are 3-D supramolecular structures constructed from bi-capped Keggin molybdenum-vanadium polyoxoanions and two different transition metal complexes. We also synthesized [Cu(2,2′-bpy)2]2[HPMo12V2O42] (4), which has been reported previously. The catalytic properties of compounds 1–4 have been investigated and we found that 1–4 are all active catalysts for the epoxidation of styrene.