Novel two-dimensional Ceria@Co, N-doped leaf-like porous carbon nanosheets (Ce-HPCNs) were fabricated using an efficient aqueous solution-mediated method. More importantly, the prepared Ce-HPCNs demonstrate even better electrocatalytic performance than the commercial Pt/C due to the synergistic effect of the oxygen buffer CeO2 with Co-Nx, and exhibit a new direction and impact in the development of new catalysts for energy applications.