Pt-grafted, hierarchical mesoporous carbon nanofibers (Pt/MPCNFs) electrocatalysts have been developed using electrospinning for high-performance PEM fuel cells. The morphological analysis of Pt/MPCNFs revealed uniformly dispersed Pt nanoparticles (2–3 nm) strongly grafted onto the hierarchical nanochannels of mesoporous carbon nanofibers (MPCNFs). Pyridinic and pyrrolic nitrogen species formed in the sp 2 graphitic structure during the carbonization process of the MPCNFs have been found to play a major role in augmentation of the triple phase boundaries in the catalyst support materials. Pt/MPCNFs exhibited outstanding electrocatalytic performance towards the oxygen reduction reaction (ORR) with a positively shifted onset potential (54 mV), half-wave potential (78 mV) and high limiting current density (4.75 mA cm −2 at 0.4 V) compared to state-of-the-art Pt/C electrocatalysts in acidic medium and they exhibited superior long-term stability (89.8% retention after 30 000 s and less change in activity after 10 000 potential sweeps). Pt/MPCNFs as a cathode catalyst yielded a maximum power density of 428.6 mW cm −2 during single cell testing, which is 2.08 times higher than a commercial Pt/C electrocatalyst. The electrochemical performance evaluation clearly implied that the unique combination of ultrathin nanofibers with a three-dimensional mesoporous structure, high electrical conductivity, enhanced specific surface area, homogeneous dispersion of Pt nanocatalysts and the presence of optimal nitrogen doping offers superior electrocatalytic activity via a favorable four-electron pathway and long-term operating stability during repeated cycles. Performance analysis in a single PEM fuel cell shows twice the power density (428 mW cm −2 ) with Pt/MPCNFs compared to commercial electrocatalyst membranes due to the effective enhancement in the triple phase boundaries, indicating that Pt/MPCNFs are potential candidates for high-performance, durable PEMFCs.