In this study, we demonstrated the needleless electrospinning of poly(vinyl alcohol) (PVA) nanofibers with two nozzles, a rotating disk and a cylinder, and examined the effect of the nozzle shape on the electrospinning process and resultant fiber morphology. The disk nozzle needed a relatively low applied voltage to initiate fiber formation, and the fibers were mainly formed on the top disk edge. Also, the PVA concentration had little influence on the disk electrospinning process (up to 11 wt %). In comparison, the cylinder electrospinning showed a higher dependence on the applied voltage and polymer concentration. The fibers were initiated from the cylinder ends first and then from the entire cylinder surface only if the applied voltage were increased to a certain level. With the same polymer solution, the critical voltage needed to generate nanofibers from the disk nozzle was lower than that needed to generate nanofibers from the cylinder. Both electrospinning systems could produce uniform nanofibers, but the fibers produced from the disk nozzle were finer than those from the cylinder when the operating conditions were the same. A thin disk (8 cm in diameter and 2 mm thick) could produce nanofibers at a rate similar to that of a cylinder of the same diameter but 100 times wider (i.e., 20 cm long). Finite element analysis of electric field profiles of the nozzles revealed a concentrated electric field on the disk edge. For the cylinder nozzle, an uneven distribution of the electric field intensity profile along the nozzle surface was observed. The field lines were mainly concentrated on the cylinder ends, with a much lower electric field intensity formed in the middle surface area. At the same applied voltage, the electric field intensity on the disk edge was much higher than that on the cylinder end. These differences in the electric field intensity profiles could explain the differences in the fiber fineness and rate of the nanofibers produced from these two nozzles. These findings will benefit the design and further development of large-scale electrospinning systems for the mass production of nanofibers for advanced applications.