Recently we have explored the magnetic functionalization of polynuclear zirconium(IV) and cerium(IV) oxide coordination clusters with paramagnetic 3d ions, motivated by their structural similarities with classical polyoxometales [1,2]. Continuing these studies, we present the synthesis and structural characterization of the novel coordination polymer {[Ce2Fe2Na2O2(ib)8(bda)2]·MeCN}n (Hib = isobutyric acid; H2bda = N-butyldiethanolamine) constructed from hexanuclear clusters (Figure).figureSingle-crystal X-ray diffraction revealed that this 1D chain polymer is constructed from hexanuclear heterometal [Ce2Fe2Na2O2(ib)8(bda)2] clusters. The {Ce2Fe2Na2O2}12+ core comprises two edge-sharing CeO9 coordination polyhedra, each containing a central 4-O2– ion which bridges peripheral Fe3+ and Na+ centers. Peripheral ligation is provided by eight isobutyrate ligands. The bda2– ligands are assumed to be fully deprotonated and act as bridging ligands via one bidentate OH group between the hexanuclear clusters. Within the core, the two central Ce centers are in the oxidation state +IV, while the two of the four terminal Fe atoms are +III. Cerium and iron oxidation states are consistent with charge balance and bond parameters, this was also confirmed by bond valence sum (BVS) calculations, which are 4.849 for Ce +IV and 3.088 for Fe +III. The magnetic properties of the compound will be discussed in an upcoming full paper.