Poly(vinylidene fluoride), PVDF, is a remarkable specialty polymer endowed with outstanding properties and involved in many applications. Its chemical structure shows some normal and defects of chaining which influence its thermal properties. This chapter supplies a non-exhaustive summary on the synthesis, properties (especially electroactive features) of PVDF, especially its electroactive features based on stimuli or when it is deformed. When suitably processed (e.g., by pooling, annealing, stretching, solvent casting or blending with another polymer), PVDF is considered as one of the most currently used ferroelectric polymers (resulting from its β crystalline polymorph), lightness and softness. More recent reports on the preparation of poly(VDF-co-TrFE), poly(VDF-ter-TrFE-ter-CTFE) or poly(VDF-ter-TrFE-ter-CFE) terpolymers (nowadays commercially available) are straightforward electroactive without any stimuli. Such PVDF and VDF-containing copolymers are innovating materials in many sectors involving internet of things, energy storage devices, smart magnetic sensors, medical applications (actuators, electrical transductions for tissue engineering, bones, muscles and nerve regeneration).