The lack of efficient electrocatalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) has been a fatal issue for the development of metal–air batteries in large-scale commercialization. In this paper, spinel CoFe2O4 (CFO) nanoparticles were successfully in situ grown onto rod-like ordered mesoporous carbon (RC) by a facile, scalable hydrothermal method, followed by annealing at different temperatures. The as-acquired CFO/RC nanohybrid pyrolyzed at 400 °C (CFO/RC-400) has a high specific surface area (150.3 m2 g−1) and two sets of uniform mesopore systems (3.38 and 19.1 nm), all of which are favorable for the improvement of the electrocatalytic activity. The hybridization of CFO nanoparticles and the RC matrix results in increased ORR and OER electrocatalytic activity of the CFO/RC nanohybrids, which is significantly superior to that of unsupported CFO nanoparticles and pure RC. CFO/RC-400 shows better catalytic activity for the ORR with a direct four-electron reaction pathway than those prepared at other temperatures in terms of the onset potential and limiting current density. Furthermore, the CFO/RC-400 nanohybrid exhibits outstanding durability for both the ORR and OER, and can outperform commercial Pt/C. The excellent bifunctional electrocatalytic activities of the CFO/RC nanohybrids are mainly owing to the hierarchical mesoporous structures of the nanohybrids and strong coupling between the CFO nanoparticles and the RC matrix.