Nowadays, the design and development of highly efficient and low–cost bifunctional electrodes for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are in urgent demand for energy conversion and storage technologies, such as fuel cells, metal–air batteries and water–splitting cells. Herein, to mitigate this challenge, a novel cost–effective flower–like Ni and N codoped hierarchical porous carbon microspheres (denoted as F-Ni/N-HPCMs) electrode has been fabricated by a simple two–step method. Benefiting from the unique structure property, the F-Ni/N-HPCMs show excellent ORR and OER performance. More importantly, H2–O2 alkaline polymer electrolyte fuel cell (APEFC) fabricated with the F-Ni/N-HPCMs cathode shows an open circuit potential of 0.84V and a high performance of 208mWcm− 2. And, the performance is better than the reported APEFCs constructed with other non–precious metal electrodes. Hence, this work provides a new strategy to fabricate high performance electrodes for fuel cell storage.