A sequential analysis using Ultra-violet Photoelectron Spectroscopy (UPS) and X-ray Photoelectron Spectroscopy (XPS) on ceria nanopowders has been implemented to identify the influence of the X-ray beam on the surface of this oxide. For the first time, UPS analysis evidenced the photoreductive effect of XPS analysis on ceria after an oxidative in situ pretreatment, leading to an overestimation of the Ce3+/Ce4+ ratio obtained by XPS. Based on this spectroscopy methodology, UPS imposes itself as a leading technique for analyzing powders with minimal impact on the authentic chemical state, thus paving the way for identifying the real ratio of Ce4+ and Ce3+ of ceria after oxidative and reductive in situ treatments.