To understand and improve the applications of titanium-oxide nanoparticles, it is extremely important to perform a detailed investigation of the surface and the interior structural properties of nanocrystalline materials, such as rutile and anatase with diameter of few nanometers. Here, x-ray absorption spectroscopy has been used to identify the local Ti environment and characterize the related electronic structure. We combine experimental results at the Ti K edge in both bulk and nanocrystal samples to determine the lattice distortion via the characteristic pre-edge features and the variation in the multiple-scattering region of the x-ray absorption near-edge structure spectra. The correlation between peak intensities and surface-to-volume ratio of nanoparticles is also discussed. © 2002 American Institute of Physics.