Exploring a cheap catalyst with effective activity for oxygen reduction reaction (ORR) to replace precious metal electrocatalysts has gained tremendous attention for several decades. In this study, we designed and synthesized cobalt and nitrogen supported on mesoporous hollow carbon hemisphere (Co/N/HCHs) nanocomposites by a facile and economical approach. Semisphere-shaped mesoporous hollow carbon is self-generated using silica particles as template, followed by a pyrolysis-etching process; and exhibits high electrical conductivity and high specific surface. The unique porous structure of carbon provides significant number of the abundant defective sites and shortens the mass transfer pathway, leading to a greatly enhanced electrocatalytic activity with mainly 4e(-) reduction. Moreover, the synergistic effects of large electrochemically active areas and good electrical conductivity, resulting from the introduction of Co and N heteroatom, are the main reason for displaying outstanding ORR activity with a high half-wave potential of 0.8 V and the electron transfer numbers of 3.89. Furthermore, an excellent long-term stability (the current density retention of 87.0%) and superb methanol tolerance in alkaline medium are achieved. Undoubtedly, this demonstrates a potential way to strategically design the non-precious metal doped carbon catalysts for wider practical applications. (C) 2020 Elsevier Inc. All rights reserved.