Electrospinning was used to fabricate mats of poly(vinyl alcohol) (PVA; M-w = 72,000 Da, degree of hydrolysis approximate to 97.5-99.5) nanofibers from PVA solutions in reverse osmotic water. The effects of solution concentration, applied electrical potential, sonication, and collection distance on morphological appearance and diameters of the as-spun fiber mats as well as those of the individual fibers were carefully investigated mainly by scanning electron microscopy. The effect of the distance from the center of the as-spun fiber mat on morphological appearance and diameters of the as-spun fibers was also investigated. The mechanical integrity of some as-spun PVA fiber mats was also investigated. At all concentrations and applied electrical potentials investigated, the average diameters of the as-spun PVA fibers ranged between 85 and 647 nm. The use of sonication to prepare a PVA solution caused the viscosity of the solution to decrease; hence, the observed decrease in the average diameters of the as-spun fibers and the average diameters of the asspun fibers were practically the same throughout the asspun fiber mat. (c) 2008 Wiley Periodicals, Inc. J Appl Polym Sci 108:969-978,2008.