Nanotechnology is ever evolving and the ability to alter material properties at the nanoscale is fascinating. Nanotechnology can give a particular material/composite by making it stronger, more durable, lighter, more flexible, better electrical conductors and many more. Electrospinning is one such way to produce ultrafine polymer nanofibers with multifunctional traits such as piezoelectricity. In the field of energy harvesting, interest in piezoelectric nanocomposites has skyrocketed. Wearable electronics, nanogenerators, mechanical actuators, and electromechanical membranes employ these materials. In this research study, nanocomposite fiber membranes of different blend ratios of PVDF, PAN, ZnO and BaTiO3 have been synthesized using electrospinning technique. The inclusions of BaTiO3 (<50 nm) and ZnO (<100 nm) nanoparticles were at nanoscales to increase the surface area and the vibration energy harvesting rates of the prepared nanocomposite fibers. This research work investigates the piezoresponse analysis of various concentration ratios of PVDF/ZnO, PVDF/BaTiO3, PAN/ZnO and PAN/BaTiO3 electrospun nanofibers. A tapping (vibration) device was designed and made for this purpose. It has been found that PVDF with 2wt% of BaTiO3 electrospun nanofiber composite generates a higher average peak output voltage of about 137V at different tapping forces along with piezoelectric hysteresis effect. Thus, the addition of BaTiO3 nanopowder to PVDF electrospun nanofibers further enhances its piezosenstivity to a greater amount. Although pure PAN nanofiber (2.72V) is not a strong piezoelectric material compared to pure PVDF (28.74V), inclusion of 2wt% of ZnO to PAN has significantly increased the PAN’s voltage generating capability (22.63V). This enhanced voltage generation capability of PVDF/BaTiO3 and PAN/ZnO nanocomposite mats are promising nanogenerators in energy harvesting applications and wearable technologies. This study may open some novel opportunities to develop a new set of vibration-based energy harvesting materials, devices, and systems in the future.