A novel hierarchical hybrid nanostructure of Co-doped ZnO NPs@rGO is successfully synthesized via a facile solution-refluxing strategy. Co0.38Zn0.62O NPs@rGO exhibits a good electrocatalytic activity for oxygen reduction reaction in alkaline electrolyte. A nearly four-electron catalytic pathway, excellent stability and methanol-tolerance capability of Co0.38Zn0.62O NPs@rGO are proved.