Rutile powder was synthesized via sol–gel processing of Tyzor TE precursor in an aqueous solution at 40°C–50°C. A suite of characterization techniques, including FTIR, Raman, X-ray, and electron diffraction, were employed to investigate the microstructural evolution. The synthesized powder was phase-pure rutile possessing high surface area (144.7 m2/g), an average pore size of 24.9 nm, and pore volume of 0.66 cm3/g. A reaction mechanism is proposed for the preferential evolution of rutile over other titania polymorphs (i.e. amorphous or anatase).