Abstract X‐ray photoelectron spectroscopy (XPS) is used for investigating the valence state of the chemical elements present in 25.5 wt.% CeO 2 −2.5 Y 2 O 3 −72 ZrO 2 plasma‐sprayed coatings as a function of the deposition temperature. Unlike the other chemical elements, cerium changes its valence state during and after the spraying process. The analysis of Ce 3d binding energies and satellite structures shows that CeO 2 after spraying is either partially reduced to Ce(III) at low deposition temperature, or remains essentially unchanged at high deposition temperature. In both cases, the presence of ZrO 2− x suboxides is found, which does not depend apparently on the cooling rate.