Catalysts for oxygen reduction reaction (ORR) play an important role in fuel cells. Developing the novel catalyst with high activity at low-cost remains a great challenge. We report the novel nanostructure (Co/Co3O4/C–N) of an interconnected nitrogen-doped carbon framework with Co/Co3O4 nanoparticles. Chitosan was used as carbon and nitrogen sources. The product, which has high BET surface area (320.5m2 g−1) shows excellent catalytic ability, stability and tolerance to methanol poisoning effects in the alkaline media for ORR. The product may also have potential applications in the fields of metal-air batteries, supercapacitors, lithium ion batteries, sensors, gas uptake, and so on.