Polyvinylidene fluoride (PVDF) boosted its technological applications because of its piezoelectric and pyroelectric properties, together with mechanical, chemical, and thermal resistance. In this review, we address the PVDF chemical structure and its synthesis procedure, also describing the occurrence of polymorphism (alpha (α), beta (β), gamma (γ), and delta (δ) of this semicrystalline polymer, and the processes involved in phase transformation that govern the adaptability of the PVDF crystalline phases and properties for several industrial uses. It can be used as a component of implants and sutures, as engineering plastic to play a structural role in aggressive environments, acting in the field of process control as a component of transducers and sensors, as well as in the synthesis of separation membranes, fuel cells, and a long list of new applications that include an important role in robotics. The main physicochemical techniques used for PVDF characterization, i.e., differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy, that highlight its unique properties, are also discussed, showing the versatility of PVDF for a range of biomedical and pharmaceutical applications.