Rational design is essential in the synthesis of electrocatalysts for the oxygen reduction reaction (ORR). Herein, we introduced zeolitic imidazolate framework-8 (ZIF-8) and polyvinyl pyrrolidone (PVP) into the electrospinning process of the polyacrylonitrile (PAN) and hemin to increase the active site loading and exposed active area of the final product with empty bead-like structures. In this method, ZIF-8 acts as a carbon skeleton to provide a rich microporous structure that can support active sites, and as a nitrogen dopant to improve nitrogen contents. PVP changes the properties of the spinning solution, adjusts the fiber morphology, and to increase the exposed area of active sites as a pore former. The obtained Feâ€"Nâ€"C ORR catalyst delivered a half-wave potential (E 1/2) of 0.924 V in a 0.1 M KOH solution and 0.77 V in a 0.1 M HClO4 solution. A homemade zinc air battery with power density of 236 mW cmâ'2 demonstrated the excellent performance of the catalyst under working conditions. [ABSTRACT FROM AUTHOR]