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N-doped graphene decorated with cobalt-based nanoparticles (Co/CoO/NG-T) were obtained via a 1,10-phenanthroline assisted pyrolysis method. The optimized Co/CoO/NG-800 showed excellent performance with E1/2, ORR of 0.82 V vs. RHE and ηOER, 10 mA cm-2 of 407 mV. A good stability was obtained with only 20 mV negative drift in the half-wave potential after 2000 cycles, and a retention rate of 94% after 5 h. The prominent performance is attributed to the electronic interaction between Co-based species and N-doped graphene, and the presence of active pyridinic-N moieties. This work provides a revealing paradigm on the design of efficient non-precious metal-based electrocatalysts.