Electrospun fibers of poly(vinyl alcohol) (PVA) and PVA/poly(4-styrenesulfonic acid) (PSSA) were obtained. By varying PVA to PSSA weight ratios, various fiber sizes and shapes were observed. The fiber diameters ranged from 176 to 766 nm, and the largest fibers were obtained from 15 wt % aqueous PVA solution. The effect of solution viscosity on fiber morphology was discussed. The presence of PSSA in electrospun fibers was confirmed by Fourier Transform Infrared spectroscopy. The PVA fibers were thermally stable up to 250 degrees C, and the PVA/PSSA fibers were stable up to approximately 150 degrees C. The water stability of the fibers was improved by heat-treatment at 120 degrees C. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012