ABSTRACT Pyroelectric energy conversion has emerged as a compelling strategy for directly transforming ambient thermal fluctuations into electrical energy. In contrast to conventional thermoelectric systems, which exploit sustained spatial temperature gradients via the Seebeck effect, pyroelectric devices utilize temperature‐dependent variations in spontaneous polarization, thereby eliminating the need for a persistent thermal differential. This unique mechanism renders pyroelectric systems particularly suitable for applications involving intermittent or dynamically varying thermal environments, spanning both sensing and energy harvesting. Among polymeric pyroelectric materials, poly(vinylidene fluoride) (PVDF) and its copolymers have attracted considerable interest owing to their mechanical flexibility, facile processability, biocompatibility, and tunable electroactivity. This review comprehensively introduces PVDF‐based pyroelectric systems, encompassing fundamental mechanisms, material engineering strategies, device architectures, and emerging applications. The principles of pyroelectricity and electro‐thermodynamic cycles are first elucidated, followed by an description of structure–property relationships in PVDF‐based polymers. Emphasis is placed on innovative device designs that integrate multiple physical effects to enhance performance. Additionally, hybrid energy harvesters, self‐powered sensors, and bioelectronic applications enabled by PVDF are explored. Finally, key challenges and future research directions are outlined to advance the development of high‐performance, multifunctional pyroelectric systems.
Wang et al. (Thu,) studied this question.