We present the formation of the largest titanium-oxo cluster, [Ti-42(mu(3)-O)(60)(OiPr)(42)(OH)(12))](6-) with the first fullerene-like Ti-O shell structure. The {Ti42O60} core of this compound exemplifies the same icosahedral (4) symmetry as C-60, the highest possible symmetry for molecules. According to the coordination environments, the Ti centers in this: cluster can be arranged into a Platonic {Ti-12} icosahedron and an Archimedean {Ti-30} icosidodecahedron. The solution stability of this duster was confirmed by electrospray ionization mass spectrometry. The spherical body of the {Ti42O60} core has an inside diameter of 1.05 nm and an outside diameter of 1.53 nrn, which could be directly visualized by high-resolution transmission electron microscopy. Our results demonstrate that titanium oxide can also form fullerene-like shell structures.