Development of efficient electrocatalysts for the oxygen reduction reaction (ORR) remains a key issue for the commercialization of metal-air batteries. In this study, the novel structured Co3O4 nanoparticles-modified [Formula: see text]-MnO2 nanorods supported on reduced graphene oxide (Co3O4-MnO2/rGO) were synthesized with varying amounts of [Formula: see text]-MnO2 via a facile two-step hydrothermal method. The relationship between the physical properties and the electrochemical results was investigated using X-ray diffraction spectrum, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, cyclic voltammograms, electrochemical impedance spectroscopy and rotating disk electrode. The as-prepared Co3O4–MnO2 nanohybrid exhibits enhanced catalytic activity for ORR under alkaline condition compared with MnO2/rGO and Co3O4/rGO. Furthermore, it mainly favors a direct 4e-reaction pathway for ORR, which is attributed to the well-designed structure, the synergistic effect between Co3O4 and [Formula: see text]-MnO2, and the covalent coupling between the Co3O4-MnO2 and reduced graphene oxide. The role of Co3O4 in Co3O4–MnO2 hybrid for catalyzing ORR also has been illustrated by varying the mass ratio of Co3O4 and MnO2, which reveals that the Co3O4–MnO2 with the ratio of 1:1 has better catalytic activity.