Defect sites play an essential role in ceria catalysis. In this study, ceria nanocrystals with well-defined surface planes have been synthesized and utilized for studying defect sites with both Raman spectroscopy and O-2 adsorption. Ceria nanorods ({110} + {100}), nanocubcs ({100}), and nano-octahedra ({111}) are employed to analyze the quantity and quality of defect sites on different ceria surfaces. On oxidized surfaces, nanorods have the most abundant intrinsic defect sites, followed by nanocubcs and nano-octahedra. When reduced, the induced defect sites are more clustered on nanorods than on nanocubes, although similar amounts (based on surface area) of such defect sites are produced on the two surfaces. Very few defect sites can be generated on the nano-octahedra due to the least reducibility. These differences can be rationalized by the crystallographic surface terminations of the ceria nanocrystals. The different defect sites on these nanocrystals lead to the adsorption of different surface dioxygen species. Superoxide on one-electron defect sites and peroxide on two-electron defect sites with different clustering degree are identified on the ceria nanocrystals depending on their morphology, Furthermore, the stability and reactivity of these oxygen species are also found to be surface-dependent, which is of significance for ceria-catalyzed oxidation reactions.