© 2022 Hydrogen Energy Publications LLCComposite membranes, which are composed of polyvinylpyrrolidone (PVP)/polyethersulfone (PES)/halloysite nanotubes (HNT), have a high potential to be an alternative candidate for proton exchange membrane fuel cell (PEMFC) applications. In this context, PVP/sulfonated PES matrix decorated by sulfonated HNT was successfully fabricated via the electrospinning method. The fabricated PEMs were characterized by SEM, FT-IR, XRD, TGA, electrochemical impedance spectroscopy (EIS), water uptake capacity, swelling property, ion exchange capacity tests, and fuel cell performance tests. The results of morphological characterization showed that smooth and bead-free alignments with randomly oriented fibers were achieved. It is found that the mass percentage of sHNT increased the thickness, and accordingly, the surface area of swelling and water uptake capacity were enhanced. Therefore, the mechanism of the proton transfer increased, and the proton conductivity values were also increased with temperature. In addition, ion exchange capacity values progressively increased as the content of sHNT enhanced up to 1%. The fabricated sPES/PVP-sHNT-1.0 membrane stood out of among other membranes higher current density of 450 mA cm−2 at 0.6 V. To sum up, these fabricated nanofibrous composite membranes showed a high potential for use as fuel cells.