Two different synthetic routes were used to synthesize three nanostructured cerium (IV) oxide powders: Two samples were obtained by precipitation from a basic solution of cerium nitrate and treated at 523 and 923 K, respectively, the third one was prepared by a microwave-assisted heating hydrolysis method and treated at 523 K. Compared with the first method, microwave synthesis has the advantage of very short reaction times and produces small particles with a narrower particle size distribution. All of these advantages can be attributed to the fast and homogeneous microwave heating which gives rise to a rapid and more simultaneous nucleation and ready dissolution of the gel. The present work focuses on the XPS analysis: The influence of the heat treatment and the preparation procedure on the surface properties are deeply investigated. Besides the wide scan spectrum, detailed spectra for the Ce 3d, Ce 4d, O 1s, and C 1s regions and related data are presented and discussed.