Multi-faceted microstructures of titanium glycolate have been produced by room-temperature polyol process in which titanium alkoxide and polymethylene glycol were mixed rigorously and then the mixture was aged to settle down as white precipitate. Depending on types of titanium alkoxides and polymethylene glycols, stirring time, and composition, a variety of polygonal microrods were generated. Unlike unidentified structures produced from polyol process at elevated temperature, the titanium glycolate products obtained at room temperature revealed well-defined rod-like or plate-like structures with polygonal cross sections. Then, as-prepared titanium glycolate microstructures were transformed into higher refractive index titania of anatase or rutile phase by annealing. The characterization of as-prepared and annealed structures was conducted using scanning and transmission electron microscopes, X-ray diffractomer, and thermal analyzer for thermogravimetry and differential scanning calorimetry. (C) 2007 Elsevier Inc. All rights reserved.