Titanium dioxide nanoparticles consisting of pure anatase, anatase-rich, brookite-rich, and pure brookite modifications were synthesized and characterized by X-ray diffraction, field emission-scanning electron microscopy and nitrogen adsorption. The phase transformations among the three modifications of TiO2 (anatase, brookite, and rutile) and the photocatalytic activities of these nanoparticles were investigated by heat treatment over the temperature range from 400 to 800 °C and by the photooxidation of methanol, respectively. Direct transformation of anatase and brookite to rutile was observed, while in the case of the anatase–brookite mixture, anatase transforms firstly to brookite and then to rutile. The photocatalytic activity measurements indicate that brookite nanoparticles exhibit higher photocatalytic activities than anatase, and a comparable activity to that of the anatase-rich nanoparticles. The phase transformations and photocatalytic results are discussed regarding their dependence on crystallite size, surface area, and phase composition.