Highly porous nitrogen doped carbon fibers like churros morphology are prepared from a simple and cost-effective fabrication process, electrospinning with bicomponent polymer consisting of polystyrene (PS) and polyacrylonitrile (PAN). From appropriate ratio of two polymer and pyrolysis at 1100 °C, newly churros morphology with extremely high surface area (1271 m2 g−1) is prepared. During carbonization, more unstable PS than PAN plays a critical role in forming such morphology by acting as sacrifice materials, thus providing additional formation of inner pores and outer etched surfaces. Furthermore, it demonstrates excellent electrocatalytic activity toward ORR, which is attributed to highly meso- and macro porous nitrogen-doped large surface area and enhanced graphitic-nitrogen groups of carbon fibers. For example, the performance of a Zn–air cell based on the nitrogen-doped porous carbon nanofibers exhibits a peak power density of 194 mW cm−2, comparable to that based on a commercial Pt/C catalyst (192 mW cm−2). Further, the generation of hydrogen peroxide ions (<20%) in a half cell is similar to that on the commercial Pt/C catalyst.