A sol-solvothermal process with the starting precursor of titanium tetrachloride and tetrabutyl titanate mixture based on benzene-water interfaces has been developed for the fabrication of nanostructured TiO2 with various morphologies. Spherical nanoparticle, free-standing nanorod and nanoflower assembled with naonrods have been prepared through the present reaction system. The sol-solvothermal synthesis of nanostructured TiO2 has been studied systematically to examine the processing parameters that control crystallite size, phase and morphology. The effects of sol process and solvothermal process on the control over the morphology of the nanostructured TiO2 have been investigated in detail. (c) 2005 Elsevier B.V. All rights reserved.