Polymeric polyvinylidene fluoride (PVDF) nanofibers have drawn more attention due to their superior mechanical strength, piezoelectric qualities, and thermal stability. PVDF is regarded as a popular fluoropolymer. It is easily processed and possesses chemical resistance to a variety of substances, including various acids, bases, organic solvents, oil, and fat. Among the most extensively studied polymers with piezoelectric characteristics is PVDF. It was noted in the literature that increasing the β-phase in PVDF crystals and fibers increased the material's electromechanical properties. The β-phase concentration of PVDF has been increased by several studies over the last few decades, utilizing a variety of processing methods and additives. Electrospinning is one of these processing techniques. The development of electrospinning technology enabled precise tweaking of the β-phase. Pure polymer materials only have a restricted number of applications because of their small β-phase percentage. To address this issue, using nanofibers (NFs) to create composite materials is an extremely attractive design strategy for piezoelectric materials. This work reviews the impact of several nanoadditives, such as metal oxides, carbon-based materials, organic and inorganic lead halide perovskites, and some other fillers, on the piezoelectric behavior of PVDF and its copolymer structure. This paper makes an effort to provide a general overview of the electrospinning procedure for PVDF, a piezoelectric polymer, as well as the approach used to characterize its β-phase and composite materials made with NFs. With an emphasis on creating a suitable crystalline structure in the PVDF material, this study seeks to give commentary from a materials chemistry standpoint.