Developing non‐noble‐metal electrocatalysts used for efficient oxygen reduction reactions (ORR) is greatly significant in the advancement of fuel cells. Herein, a novel electrocatalyst Co/N−G has been synthesized via simply pyrolyzing the mixture of amino phenanthroline (NH2‐Phen), graphene oxide and cobalt salt. The microstructure of the catalyst has been characterized by using HADDF‐STEM, XRD, Raman and XPS, the results indicate that the precursor complex has formed Co nanoparticle during the high‐temperature pyrolysis process. The obtained catalyst of Co/N−G shows relatively good ORR catalytic activity (E1/2=0.80 V) and almost 4e− oxygen reduction pathway in alkaline. In addition, the Co/N−G catalyst shows better methanol‐tolerant ability and longer‐term stability than Pt/C catalyst.