Metal-organic framework (MOF)-derived transition metal/metal oxide-carbon hybrids are promising cost-effective electrocatalysts to replace noble metal catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Herein, Co@CoO@Co3O4-N/C was prepared by two-step thermal treatment of Co-MOF ([Co(INA)(2)]center dot 0.5EtOH) (INA: isonicotinic acid). Firstly, Co-MOF, as precursor, was pyrolyzed at different temperatures in N-2 atmosphere to obtain Co-N/C-T (T = 700, 800, 900 degrees C) materials among which Co-N/C-800 shows remarkably high ORR activity. After oxidation treatment, Co-N/C-800 is transformed into Co@CoO@Co3O4-N/C which exhibits enhanced electrocatalytic activities for both ORR and OER. The as-obtained Co@CoO@Co3O4-N/C has more positive onset potential (-0.136 V vs. Ag/AgCl) and higher limit current density (4.9 mA cm(-2)) than Co-N/C-800 (-0.143 V vs. Ag/AgCl and 3.9 mA cm(-2)), as well as better tolerance to methanol and stability (80.0%) than those of Pt/C (63.2%) for ORR. Co@CoO@Co3O4-N/C also displays outstanding OER performances, with lower overpotential (450 mV) than that of Co-N/C-800 (492 mV) at a current density of 10 mA cm(-2). The excellent electro-chemical performance of Co@CoO@Co3O4-N/C can be ascribed to uniformly dispersed Co-N-x active sites, strong synergistic effects between N-doped carbon support and Co@CoO@Co3O4 as well as ordered mesoporous structure, boosting mass transfer and accelerating electrocatalytic reaction. (C) 2018 Elsevier Inc. All rights reserved.