Ce-based materials have been widely used as a radical scavenger to improve the chemical durability of the membrane in polymer electrolyte fuel cells; however, any negative effects from Ce ions on power performance have not been reported as an issue before except for ionomer contamination by Ce3+. Herein, we propose and experimentally demonstrate the detrimental effect of Ce4+ on the Pt/C catalyst. Due to the strong oxidation power of Ce4+, Pt and carbon are subjected to oxidative decomposition under contact with Ce4+. Based on the electrochemical and spectroscopic analyses of the PVC stored in Ce3+ and Ce4+ electrolyte, Pt2+ dissolution and carbon corrosion by Ce4+ are verified. As a result, the active surface area and oxygen reduction reaction activity of PVC are considerably reduced after storage in the Ce4+ electrolyte. Additionally, at the membrane electrode assembly level, it is demonstrated that the Ce4+ leached out from the CeO2 causes a significant power performance decay along with the loss of the active surface area and an increase in the charge transfer resistance. The newly-found detrimental effect of Ce4+ on the PVC catalyst emphasizes the importance of preventing Ce4+ dissolution to improve the membrane durability by Ce-containing radical scavengers.