Polyvinylidene fluoride (PVDF) has become a cornerstone in the advancement of flexible and wearable electronics due to its exceptional mechanical flexibility, chemical stability, and electroactive behavior. This chapter presents a thorough exploration of PVDF’s molecular structure, processing methods, and integration strategies that underpin its use in self-powered sensors, energy harvesting devices, and biomedical applications. Special attention is given to the latest progress in fabricating PVDF-based thin films, nanofibers, and composites, as well as their deployment in health monitoring, human–machine interfaces, and smart textiles. The discussion extends to the biocompatibility and long-term durability of PVDF, emphasizing its reliability for continuous operation in real-world environments. The chapter also addresses current challenges such as enhancing stretchability, improving device integration, and advancing sustainable practices while highlighting innovative solutions and future research directions. Altogether, this work underscores PVDF’s transformative impact on next-generation wearable technologies and its ongoing role in shaping the future of flexible electronic systems.