An electrocatalyst support material based on hierarchical mesoporous hollow carbon nanofibers ( m PHCNFs) has been developed by co‐axial electrospinning and has been deployed for the fabrication of polymer electrolyte membrane fuel cells (PEMFCs). The synergistic effect of a high specific surface area (780 m 2 /g), homogeneous formation of mesopores (20–50 nm), and hollow nanochannels in the carbon nanofiber matrix lead to the uniform distribution of Pt electrocatalysts. XPS analysis revealed that the presence of nitrogen species in the mesoporous hollow carbon nanofibers in the form of pyridinic, pyrrolic, and quaternary nitrogen atoms played a crucial role in the augmentation of triple‐phase boundaries. Pt/ m PHCNFs exhibited superior electrocatalytic activity towards the oxygen reduction reaction with a positively shifted onset potential (62 mV) and half‐wave potential (86 mV) as well as a high limiting current density (4.76 mA/cm 2 ) compared to commercial electrocatalysts. The Pt/ m PHCNFs catalyst exhibited excellent stability in acidic medium and showed only 23 mV loss in the half‐wave potential; whereas, Pt/CNFs (35 mV) and Pt/C (77 mV) exhibited a much higher shift in half‐wave potential. The PEMFC testing of the membrane electrode assembly based on Pt/ m PHCNFs (411 mW/cm 2 ) revealed a superior performance compared to Pt/CNFs (297.4 mW/cm 2 ) and Pt/C (212.8 mW/cm 2 ). This method can offer an effective strategy for the development of durable, low‐cost, and high‐performance PEMFCs.