Polyacrylonitrile (PAN) fiber web was manufactured via electrospinning. The applied voltages were controlled at 20 and 25 kV during the electrospinning. In order to study the influences of the applied voltage and the collection area on the diameter and the crystallinity of the resulting fiber, specimens were obtained at the centers and boundaries of the collected web and characterized using SEM and XRD. The applied voltage showed a significant effect on the crystallinity, which increased with the applied voltage. Regardless of the applied voltage, the crystallinity of the fiber collected at the center showed higher values than the one in the boundary. The changes in the crystallinity can be attributed to the strength of the attractive force between the spinline and the collector, and the vaporization of the solvent from the spinline.