To investigate the relationship between the size and structure of TiO(2) nanoparticles, three size-selected samples of TiO(2) nanoparticles were prepared via a hydrolysis method that uses Ti[OCH(CH(3))(2)](4) as the starting material. The structures of the nanoparticles were characterized using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS). Analysis of the XRD patterns and of the TEM images showed that the samples were dispersed, with an average particle size of approximately 30 nm (sample A), approximately 12 nm (sample B), and approximately 7 nm (sample C). Their X-ray absorption spectra indicate that samples A and B have an anatase structure, whereas sample C has a structure very similar to that of the TiO( 2) II phase, which generally arises only under high-pressure conditions. This difference can be attributed to size-induced radial pressure within the smaller nanoparticles, which plays an important role in the phase of TiO(2) nanoparticles in sample C.