The process parameters were studied during the fabrication of polyvinyl-alcohol (PVA) nanofibers via electrospinning. The factorial experiment design model described electrospinning as an efficient, versatile approach for fabricating nanofibers. The mathematical model was developed by considering the effect of voltage, concentration, the distance between the pin and the collector, and flow rate, respectively. The influence of these parameters on the diameter and morphology of obtained PVA fibers was investigated by transmission electron microscopy (TEM). It was found that the concentration had the most significant influence on the polymer fiber diameter.