The electrospinning process successfully produced zinc oxide and polyvinylpyrrolidone (PVP) composite nanofibers. For electrospinning, a mixture of Polyvinylpyrrolidone (PVP) as a binder, zinc acetate as a precursor, and dimethylformamide (DMF) as solvent was used. The impact of high voltage on fibers diameter were investigated. The calcination process with a temperature of 350°C for 2hr was conducted to remove the PVP components. Because PVP decomposes during calcination, ZnO+PVP nanofibers can be transformed into pure wurtzite phase ZnO nanofibers with smaller diameters and better homogeneity. Field Effect Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD) studies, and Energy-dispersive X-ray spectroscopy (EDS) were used to examine the morphological and structural properties of the as-spun and calcinated ZnO/polyvinylpyrrolidone composite fibers. Compared to the initial sample created with a voltage of 24KV, the diameter of ZnO nanofibers was reduced to 23.31nm after calcination as the high voltage parameter increased to 32KV. According to the findings, the diameter of the nanofibers altered when the high voltage was applied.