In this study, polyvinylidene difluoride (PVDF) is doped with different volume levels (10, 20, 30 vol %) of lead zirconate titanate (PZT), and neat PVDF (undoped) electrospun nanofibres are prepared by aligning them through the electrospinning process with a rotating drum collector. All of the produced nanofibres are characterized by X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), and Fourier Transform Infrared spectroscopy (FTIR). The piezoelectric nanogenerator (PEN) devices are fabricated by placing the PVDF/PZT electrospun nanofibres as the dielectric material between two conductive plates. The vibrational energy harvesting analyses of the PEN are defined by taking measurements under various resistive loads. At 15 Hz excitation frequency, the maximum output power of PEN with PVDF+10 vol %PZT reaches 6.35 mu W by increasing the power to 85% under a resistive load of 1M Omega, while the PEN with beta-PVDF has the electrical power of 3.44 mu M at the same load. The PEN based energy generation is a promising source of clean energy generation from mechanical vibrations for powering portable microelectronic applications without an external power supply.