The new compound Ce20Ti11S44O6 crystallizes in space group D-2h(13)-Pmmn of the orthorhombic system with two formula units in a cell of dimensions a = 22.4628(8), b = 14.2531(7), and c = 10.382(2) (T = 293 K). Isostructural with La20Ti11S44O6, this Compound comprises (2)(infinity)[(Ti4S2O4)(TiS6)(2/2)(Ti2S10)(2/2)] layers of [Ti(4)S2O(4)] clusters linked together by edge-sharing, rutile-like chains of TiS6 octahedra. An additional pair of corner-sharing, oxygen-bridged, Ti-centered octahedra are found separated from the covalently-bonded layers. Charge balance restrictions require that Ti atoms be in the mixed oxidation states of 3+ or 4+. The seven crystallographically independent Ce atoms are found in three different coordination polyhedra.