Polyvinylidene fluoride (PVDF) is among the most attractive piezo-polymers due to its excellent piezoelectricity, lightweight, flexibility, high thermal stability, and chemical resistance. PVDF can exist under different forms of films, membranes, and (nano)fibers, and its piezoelectric property related to its β phase content makes it interesting for energy harvesters and wearable applications. Research investigation shows that PVDF in the form of nanofibers prepared by electrospinning has more flexibility and better air permeability, which make them more suitable for these types of applications. Electrospinning is an efficient technique that produces PVDF nanofibers with a high β phase fraction and crystallinity by aligning molecular dipoles (–CH2 and –CF2) along an applied voltage direction. Different nanofibers production techniques and more precisely the electrospinning method for producing PVDF nanofibers with optimal electrospinning parameters are the key focuses of this paper. This review article highlights recent studies to summarize the influence of electrospinning parameters such as process (voltage, distance, flow rate, and collector), solution (Mw, concentration, and solvent), and ambient (humidity and temperature) parameters to enhance the piezoelectric properties of PVDF nanofibers. In addition, recent development regarding the effect of adding nanoparticles in the structure of nanofibers on the improvement of the β phase is reviewed. Finally, different methods of measuring piezoelectric properties of PVDF nanofibrous membrane are discussed.