A biphasic sol-gel method was introduced to reduce a high hydrolysis rate of metal alkoxides and control a morphological evolution of metal oxides. Titanium tetraisopropoxide (TTIP) was dissolved in an organic solvent which was immiscible with water. The TTIP solution was then contacted with water or pHcontrolled aqueous solutions to promote the hydrolysis and the polycondensation reaction through the mass transfer across the organic/aqueous interface. Anatase TiO 2 was formed in any conditions employed in the present work at reaction temperatures of 80 • C or below. The morphology of TiO 2 particles obtained was largely dependent on the kind of organic solvents. It was basically the aggregation of nanoparticles to give submicrometer-sized secondary particles with or without a regular shape. Heptane was found to be suitable to obtain spherical TiO 2 large particles, which were evaluated as a photoanode material in dye-sensitized solar cells. Actually the large TiO 2 particles worked well as the light scattering layer when applying them to a double-layered phtoanode, which showed an energy conversion efficiency of 5.67% with a high short-circuit photocurrent density of 14.1 mA cm −2 .