In this review paper, we will talk about the electroactive phases of Poly (vinylidene fluoride), PVDF, their identification, processing, and applications. We will find and tabulate the problems that occur in the identification of different phases of PVDF. PVDF exists in five phases α, β, γ, δ, and ε-phases. These electroactive properties have applications in energy generation and storage, biomedical applications, smart scaffolds, sensors and actuators, nanofilms, filters, and spin-valve devices. We will also discuss the different processing methods of β- and γ- phases. PVDF and its copolymers have significantly large applications. Also, we will discuss the conclusions of different techniques to identify; quantitively and qualitatively the different polymorphs of the PVDF. There are different methods of processing these polymorphs, phase transition method can be used to get one polymorph from another. And an insight into the development and utilization of polymorphs of PVDF.