A core-shell Pt/C@NCL300 catalyst with an accessible layer was designed to recover lost ORR activity and was constructed via a one-step self-assembly process in this paper. A thin porous layer derived from Nafion was first formed on the surface of Pt/C catalyst to create a shell. This first coating successfully separated the Nafion and Pt particles in the catalysts and reducing the negative impact of Nafion on ORR activity and enhancing the fuel cell performance. The newly fabricated Pt/C@NCL300 catalyst exhibited much higher specific activity than the original Pt/C catalyst in RDE tests under the same conditions and were comparable to the activity of Pt/C electrode without Nafion poisoning. Moreover, the fuel cell with Pt/C@NCL300 catalyst exhibited a higher power density without an obvious increase in proton transport and O(2)transport resistance compared to that of a Pt/C fuel cell with a low Pt loading. This result indicates that coating the Pt/C catalyst with a layer accessible for oxygen and protons is a promising way to effectively promote Pt-based catalysts that work under normal operating conditions.