Mono-substituted and sandwich-type copper substituted polyoxoanions ([PW11CuO39]5− and [Cu4(H2O)2(PW9O34)2]10−) were studied as catalysts for the epoxidation of cyclooctene and geraniol, using the green oxidant H2O2, with the results suggesting good efficiency at room temperature. High selectivity and reasonable conversion data were found after the first minutes of reaction. The copper centre may be responsible for this performance and our on-going research focuses in the preparation of new materials incorporating copper into polyoxometalates (POMs). In this context, we have also isolated a new crystalline dimeric sandwich-type polyoxocoppertungstate {H7.05[Cu3WO(H2O)(CuW9O34)(Cu0.6W9O34)]}7.75−. This compound was isolated as potassium salt and structurally characterized by FTIR and single-crystal X-ray diffraction (XRD). The polyoxoanion is composed by the [CuW9O34]12− and [Cu0.6W9O34]12.8− anionic fragments, joined together by a rhomb-like arrangement of three Cu2+ and one W6+ metallic centres, all exhibiting octahedral coordination geometries.