Fuel cell technology is at the forefront of sustainable energy solutions, and polyvinyl alcohol (PVA) membranes play an important role in improving performance. This article thoroughly investigates the various varieties of PVA membranes, their production processes, and the numerous modification tactics used to solve inherent problems. Various methods were investigated, including chemical changes, composite blending, and the introduction of nanocomposites. The factors impacting PVA membranes, such as proton conductivity, thermal stability, and selectivity, were investigated to provide comprehensive knowledge. By combining various research threads, this review aims to completely investigate the current state of PVA membranes in fuel cell applications, providing significant insights for both academic researchers and industry practitioners interested in efficient and sustainable energy conversion technologies. The transition from traditional materials such as Nafion to PVA membranes has been prompted by limitations associated with the former, such as complex synthesis procedures, reduced ionic conductivity at elevated temperatures, and prohibitively high costs, which have hampered their widespread adoption. As a result, modern research efforts are increasingly focused on the creation of alternative membranes that can compete with conventional technical efficacy and economic viability in the context of fuel cell technologies.