In this study, we report on the discovery, fabrication, properties and fuel cell performance of Nafion nanofibers. Fibers of Nafion on the order of 50 nm in diameter were discovered in fuel cell electrodes and were found to have an impact on fuel cell performance. Therefore, we explored the fabrication of nanofiber-based electrodes. High purity (99.9 wt%) Nafion nanofibers were produced via electrospinning and the proton conductivity of a single Nafion nanofiber was an order of magnitude higher than Nafion bulk films. The fabrication and testing of membrane electrode assemblies with nanofiber-based electrodes is currently under exploration.