Electroactive Properties of PVDF‐Based Ferroelectric Polymers: A Review

ABSTRACT With the rapid advancement of intelligent technologies, the demand for flexible electronic devices has grown increasingly urgent. In particular, intelligent materials capable of directly performing functions such as sensing, actuation, and temperature regulation under an applied electric field are essential for achieving device miniaturization, structural integration, and high energy‐utilization efficiency. Poly(vinylidene fluoride) (PVDF)‐based ferroelectric polymers, due to their diverse chain conformations, can exhibit piezoelectricity, deformation, and electrocaloric effects under an electric field, thereby demonstrating significant potential for applications in sensors, actuators, and solid‐state refrigeration. To meet the stringent requirements of advanced applications, various strategies—including chemical modification, physical blending, and processing optimization—have been employed to enhance their performance, yielding remarkable improvements. This review provides a comprehensive overview of PVDF‐based ferroelectric polymers across three major fields: piezoelectric effect, electro‐actuation effect, and electrocaloric effect. The discussion encompasses fundamental principles, approaches to modification, and representative device implementations, while highlighting the progress and technological significance of related research. Finally, the existing limitations and future challenges in this field are analyzed.