Pt-CeOx interface on Pt electrodes was prepared for improvement of both oxygen reduction reaction (ORR) activity of Pt cathode and CO tolerance of Pt anode. The surface of Pt-CeOx nano-particle/C electrode mainly consists of metallic Pt, ionized Pt (i.e. Pt2+) and Ce3+ species. The ORR activity on Pt was improved by the formation of Pt-CeOx interface. In-situ XAFS analysis suggests that cerium oxide surface in the Pt-CeOx/C was oxidized instead of Pt surface by electrochemical redox reaction of CeOx at room temperature. This suggests that the Pt-CeOx interface plays key role for improvement of cathode performance. Also, CO tolerance of Pt was improved by the formation of aforementioned interface. The improvement of CO tolerance of Pt was also observed by using in-situ IR analysis. Based on all experimental data, it is concluded that the design of defect structure in Pt-CeOx provides us opportunity to make the breakthrough electrodes for fuel cell application.