© The Author(s) 2022.The piezoelectric vibration energy harvesting performance of an electrospun poly(vinylidene fluoride) (PVDF)/Barium Titanate (BaTiO3) nanocomposite piezo polymer nanogenerator was investigated in this study. To obtain the highest piezoelectric output value, electrospinning was performed using four distinct solvent volume ratios of Acetone/Dimethylformamide (DMF) of 0:10, 2:8, 4:6, and 6:4 and three different PVDF weight percent polymer concentrations of 10, 15, and 20. Additionally, three distinct BaTiO3 addition weight percents of 5, 10, and 15 were investigated. The optimal concentration of PVDF (15 wt.%) was combined with a 6:4 volume ratio of Acetone/DMF to form a nanocomposite piezo polymer nanogenerator. The morphology and crystalline structure of PVDF and PVDF/BaTiO3 were analyzed using Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) techniques. Nanocomposite piezo polymer nanogenerator was manufactured to harvest energy from vibration. A cantilever beam was developed without a tip mass type system for piezoelectric energy harvesting tests. The highest piezoelectric power output was obtained as 0.243 μW (15 wt.% PVDF and 5 wt.% BaTiO₃), Acetone/DMF (6:4 vol./vol.)) under 10 MΩ at the 15.7 Hz resonance frequency. The morphology of electrospun nanofibers has a significant impact on the piezoelectric performance of a nanocomposite piezo polymer nanogenerator at high-amplitude vibration.