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A complex rare-earth tungstate structure, present in a two-phased powder, was solved by electron diffraction, precession and high-resolution electron microscopy. The orthorhombic space group Pbnm and the atomic positions deduced from X-ray diffraction experiments were confirmed for Ce10W22O81. A C2/c monoclinic superstructure, with cell parameters a = 7.8, b = 36.1, c = 22.2 Å and β = 100.2°, was shown and attributed to a partial oxidation of Ce3+ leading to interstitial oxygen ions.