We report a novel approach to the instantaneous photoinitiated synthesis of mixed anatase-rutile nanocrystalline TiO2 thin films with a three-dimensional nanostructure through pulsed white light irradiation of photosensitive Ti-organic precursor films. Pulsed photoinitiated pyrolysis accompanied by instantaneous self-assembly and crystallization occurred to form graphitic oxides-coated TiO2 nanograins. Subsequent pulsed light irradiation working as in situ pulsed photothermal treatment improved the crystalline quality of TiO2 film despite its low attenuation of light. The non-radiative recombination of photogenerated electrons and holes in TiO2 nanograins, coupled with inefficient heat dissipation due to low thermal conductivity, produces enough heat to provide the thermodynamic driving force for improving the crystalline quality. The graphitic oxides were reduced by pulsed photothermal treatment and can be completely removed by oxygen plasma cleaning. This photoinitiated nanofabrication technology opens a promising way for the low-cost and high-throughput manufacturing of nanostructured metal oxides as well as TiO2 nanocrystalline thin films.