Reversible surface segregation of Pt in Pt 3 Au/C catalysts was accomplished through a heat treatment under a CO or Ar atmosphere, which resulted in surface Pt segregation and reversed segregation, respectively. The Pt-segregated Pt 3 Au/C exhibited a significantly improved oxygen reduction reaction (ORR) activity (227 mA/mg metal ) compared to that of commercial Pt/C (59 mA/mg metal ). For the Pt-segregated Pt 3 Au/C, the increased OH-repulsive properties were validated by a CO bulk oxidation analysis and also by density functional theory (DFT) calculations. Interestingly, the DFT calculations revealed that the binding energy for Pt-segregated Pt 3 Au (111) surfaces was 0.1 eV lower than that for Pt (111) surfaces, which has been previously reported to exhibit the optimum OH binding energy for the ORR. Therefore, the reversible surface segregation is expected to provide a practical way to control the surface states of Pt−Au bimetallic catalysts to enhance ORR activity. In addition, the Pt-segregated Pt 3 Au/C showed excellent electrochemical stability, as evidenced by its highperformance retention (96.4%) after 10 000 potential cycles, in comparison to that of Pt/C (55.3%).