Vanadium complexes bearing easily synthesized, differently functionalized salen and salphen ligands were prepared and tested for their ability to catalyze the cycloaddition of carbon dioxide to epoxides resulting in cyclic organic carbonates. The reactivity of the prepared catalysts dramatically increases when a coordinating hydroxyl group is present as a substituent in the organic epoxide. The commercially available [VO(acac)2] complex was used as reference compound, and, in this case, we found that V10O26⋅(NBu4)4 was formed during the catalytic reactions. This compound, characterized by X-ray diffraction analysis, is likely the active catalyst, and it results in significantly better yields of cyclic carbonates compared to those obtained with Schiff base containing vanadyl complexes. The high activity of the mixed polyoxo vanadyl-vanadate complex marks it as a powerful catalyst within the context of CO2 fixation chemistry.