The first disiloxanediolate complexes of cerium(IV) are reported. Starting from the readily available precursor ((BUO)-B-t)(3)Ce-IV(NO3)(THF)(2) (1), we prepared the novel heterobimetallic compounds [{(Ph2-SiO)(2)O}{K(THF)(2)}](2)Ce((OBU)-B-t)(2) (2) and [{(Ph2SiO)(2)O}(2){(DME)-KOt-Bu}{(Ph2SiO2)K}Ce](2) (3) and structurally characterized them by X-ray diffraction.