Polymer electrolyte membrane fuel cells (PEMFCs) provide a renewable source of energy through the redox reaction of hydrogen and oxygen gas; however, operation relies on a costly platinum catalyst layer. This study investigates how electrospun catalyst layers may be employed to increase the surface area:volume ratio for catalysis to optimize PEMFC performance. When preparing electrospinning solutions, several base polymers were evaluated in varying concentrations to optimize fiber formation, with poly(acrylic acid) found to be preferable at a 12 wt% concentration. Ultimately, PEMFCs with electrospun catalyst layers achieved a 108% increase in power output compared to those air-sprayed.