Novel poly(vinyl alcohol) (PVA) nanofiber mats were prepared for the first time through heterogeneous saponification of electrospun poly(vinyl acetate) (PVAc) nanofibers. The effect of varying the saponification conditions, including temperature, time, and concentration of the alkaline solution, on the morphology of the saponified PVA fibers were evaluated by field-emission scanning electron microscopy. At 25 degrees C, the saponified PVA fibers exhibited a broad diameter distribution. The average fiber diameter, however, was found to decrease with increasing saponification temperature. When the saponification time was increased from 6 to 30 h, the average fiber diameter decreased gradually from 1540 to 1060 nm. In addition, the fiber diameter and morphology were also affected by the concentration of the alkaline saponification solution. The most optimal conditions for fabrication of thin, uniform, and smooth PVA nanofibers corresponded to an alkaline solution containing 10 g each of NaOH, Na2SO4, and methanol per 100 g of water, a temperature of 25 degrees C, and a saponification time of 24 h.