X-ray absorption spectroscopy has been used to study the structural and electronic properties of cerium atoms in nanocrystalline cerium oxide. These nanocrystalline cerium oxides were prepared by precipitation followed by the aging process. To increase the particle size, the as-prepared cerium oxides were calcined at various temperatures. The nanocrystalline phase was retained, even when the samples were calcined at 6003C. The analyses of X-ray absorption near edge structures (XANES) for cerium oxides show that the increase in the relative intensity of the transition to 2p4 f 1 5d*L 5nal state and its transition energy shifts toward higher energy are due to the increase in covalence between cerium and oxide ligands with increasing particle size. The extended X-ray absorption 5ne structure (EXAFS) results for cerium oxide show that the third Ce+O shell is degraded and the coordination number around cerium is decreased, resulting in a decrease in the bond distances of R Ce+O and R Ce+ Ce for particle size ( (15 nm. However, when the particle size is increased, the third Ce+O shell started growing and the coordination number around cerium attained normal coordination. The present results provide evidence for the formation of nanocrystalline cerium oxide prepared by precipitation followed by the aging process.