Over the past several decades, there has been a significant surge in interest regarding the use of organic–inorganic hybrid polymers and nanocomposite membranes. The reasons for this are improved attributes, reduced costs, and the additional stability the influence membrane provides. This Review outlines the various techniques and methodologies used to prepare Nafion and its composites, delineating the promising benefits of the electrospinning process. Electrospinning has emerged as a versatile and promising technique for fabricating nanofibers with unique properties and wide-ranging applications. This study explores the electrospinning of Nafion, a perfluorosulfonic acid polymer widely known for its exceptional proton conductivity and chemical stability, into nanofibrous structures, unlocking new possibilities yet unknown features of its inherent properties. The morphology and chemical structure of the resulting nanofibers is analyzed. A thorough bibliographic analysis of electrospun Nafion was presented using the PRISMA approach for methodically presenting the report. Network visualization of connected authors and categorizing application-specific publications are also discussed. Moreover, the electrospinning parameters and blends are systematically investigated to optimize the production of Nafion nanofibers for various applications in fuel cells, water treatment, actuators, sensors, and energy harvesting. The challenges involved in electrospinning Nafion, Nafion nanocomposites, and their variants are also presented, with a discussion delineating the future scope. This work concludes by emphasizing the interdisciplinary character of the Nafion polymer and its composites, connecting materials science and the intricate issues presented by various sectors.