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A new 1:2-type inorganic–organic hybrid CuⅡ–CeⅢ heterometallic germanotungstate(GT)derivative KNa2H7[enH2]2[Cu(en)2(H2O)]2[Cu(en)2]2{Cu(en)2[Ce(α-GeW11O39)2]2}·14H2O(1)(en = ethylenediamine)was obtained by simultaneously introducing Cu2+and Ce4+cations to the trivacant Keggin-type [A-α-GeW9O34]10– system in the help of extra Na2WO4·2H2O and en ligand under hydrothermal conditions and was further characterized by elemental analyses,IR spectrum,thermogravimetric analysis and single-crystal X-ray diffraction.