A novel electrochemical catalyst of phosphorus and nitrogen dual-doped cobalt-based carbon nanofibers (Co-N-P-CNFs) is prepared by a facile and cost-effective electrospinning technique. Excellent features of the porous carbon nanofibers with large amounts of Co atoms, N/P-doping effect, abundant pyridinic-N and Co-N-x clusters as catalytic active sites, and the advantages of the structure and composition result in a high catalytic efficiency. In alkaline or acidic media, Co-N-P-CNFs exhibits remarkable electrocatalytic activities and kinetics for oxygen reduction reaction (ORR), superior methanol tolerance and stability, and a similar four-electron pathway. In addition, Co-N-P-CNFs also shows excellent performance for hydrogen evolution reaction (HER), offering a low onset potential of -0.216 V and a stable current density of 10 mA cm(-2) at potential of -0.248 V. The mechanism of ORR and HER catalytic active site arises from the doping of N/P atoms in the Co-based CNFs, which is responsible for the excellent electrocatalytic performance. Due to the excellent catalytic efficiencies, Co-N-P-CNFs act as a promising catalyst material for fuel cells and water splitting technologies. Crown Copyright (C) 2016 Published by Elsevier B.V. All rights reserved.