Aqueous titanium citrate solutions were prepared from the reaction of citric acid with titanium 2-propoxide in a range of molar ratios. Solutions containing two or fewer citrates per titanium resulted in the slow crystallization of an insoluble titanium oxo-citrate complex. Single-crystal X-ray analysis identified the species as Ti8O10(citrate)(4)-(H2O)(12).14H(2)O.3HOPr(i), crystallized in the tetragonal space group l4(1)/a, with a = 30.775(7) Angstrom, c = 14.528(7) Angstrom, V = 13 759(8) Angstrom(3), and Z = 8. The trianionic citrate ligands supply both carboxylate and alkoxide coordination and stabilize the structure using simultaneous chelating and bridging modes of attachment. The compound is a neutral species, exhibiting titanium in three contrasting environments. Laser Raman microscopy and C-13 CPMAS solid-state NMR data were consistent with those of the X-ray crystal structure. When exposed to air, the crystals rapidly lost water and became a powder. The dehydrated powder was noncrystalline to X-rays and insoluble, but C-13 NMR results demonstrated retention of the carboxylate linkages.