Dicerium(IV) tetrachromate(VI) dihydrate, Ce2(IV)(CrO4)4.2H2O, has been prepared from an acidic aqueous solution at room temperature. Its novel crystal structure, which was solved from single-crystal X-ray diffraction data, is built from isolated CrO4 tetrahedra and isolated Ce(O,H2O)n (n = 8 and 9) polyhedra. All atoms are in general positions. The mean Ce-O and Cr-O bond lengths are 2.358 and 1.651 A, respectively. Comparisons are drawn with the structure of Ce(IV)(CrO4)2.2H2O.