In this work, a prospective study on the current uses and applications of polyvinyl alcohol (PVA) nanofibrillar materials is presented. Polyvinyl alcohol is a synthetic polymer that has gained attention for its biodegradability and sustainable qualities under certain conditions. It has become a valuable material in various fields, including innovative food packaging, advanced hydrogen fuel cells, and sophisticated medical applications such as wound dressings and tissue engineering scaffolds. First, the theoretical background is studied in detail to understand the structure–property relationships that govern PVA performance, examining its essential properties intrinsically linked to its structural features, such as crystallinity, mechanical properties, and bio-sustainability. Then, the main processing parameters dictating nanofibrillar morphology and the factors and parameters that may control the morphological characteristics of PVA-based materials to favor the formation of nanofibers are focused on, with particular emphasis on the electrospinning (ES) and solution blow spinning (SBS) techniques. Finally, to give consistency on the practical feasibility of both approaches, PVA nanofibers were experimentally fabricated under the optimized ES and SBS conditions established herein. Morphological, structural, and thermal characterization of the resulting materials was carried out to elucidate the differences between the two processing techniques. Ultimately, this article discusses the future research directions to address the current challenges and prospective ways to fabricate PVA nanofibrous materials for potential biomedical applications.