Hao Zhang, Xu Ji, Zhen Wang, Senyao Tang, Zhaokun Wang, Weibin Zhu
Abstract Flexible piezoelectric materials have emerged as attractive options for self‐sustaining systems, due to superior mechanical compliance, environmental adaptability and efficient transduction of mechanical to electrical energy. Among these, polyvinylidene fluoride (PVDF) and its copolymers exhibit unparalleled advantages in wearable electronics and energy harvesting applications, attributable to their pronounced piezoelectric properties, in conjunction with high flexibility, low density, chemical stability, and facile solution processability. This review introduces PVDF‐based devices through various material strategies, including piezoelectric ceramics, piezoelectric nanofillers like BaTiO 3 and ZnO, and non‐piezoelectric doping. It also systematically summarizes recent advances in hierarchical structural design, microstructure regulation, and ionic hydrogel structural modulation, as well as intelligent manufacturing techniques of PVDF‐based piezoelectric devices. Additionally, particular emphasis on their state‐of‐the‐art applications in wearable biomedical engineering, self‐charging energy storage, and other intelligent monitoring are placed. Furthermore, the current outlooks—such as long‐term operational stability, innovative materials and structures, artificial intelligence (AI), integrated smart systems, and industrialization—are critically discussed. Given the promising prospects of PVDF‐based materials for health management, intelligent connected systems, and sustainable energy technologies, this review seeks to provide a comprehensive theoretical foundation and technical reference for elucidating the structure‐function‐property relationships and advancing the multifunctional integration in next‐generation electronic platforms.