The attractive dielectric poly(vinylidene fluoride) (PVDF) and its copolymers are well confirmed possessing the highest electroactive response including dielectric constant, piezoelectric and ferroelectric effects, which have increasingly wide range of applications such as in energy transfer, energy generation and storage, monitoring and control, and include the development of capacitors, sensors, actuators and so on . In this study, by clarifying the reliability of dielectric performances on their crystal phase structure of various PVDF polymers, the different physical and chemical fabricating ways to achieve different forms of PVDF samples such as linear polymers, ferroelectrics, and relaxor ferroelectrics were identified and quantified. In addition, many recent advances in the PVDF‐based polymer dielectrics and some developed applications of these polymers are presented, which gives a reference in academic and engineering area to select an appropriate PVDF series dielectric polymer.