Polyvinyl alcohol (PVA) fibrous membranes were generated by elestrospinning 10% aqueous PVA solutions then rendered water insoluble by reactions with difunctional reagents. The as-electrospun PVA fibers were semi-crystalline as evident by melting behavior (T-m = 190 degrees C Delta H-m = 39 J/g) and wide angle x-ray diffraction (peak at 2 theta = 20 degrees). Chemical reactions with glutaraldehyde in either aqueous sodium sulfate (GA/Na2SO4) or ethanol (GA/EtOH) and polyethylene glycol (PEG) diacylchloride in 1: 1 (v:v) toluene/pyridine produced crosslinked PVA with varied effects on the crystalline structure of the fibers. The fiber diameters remained in the submicrometer range. Among all crosslinking agents and conditions studied, reaction with shorter PEG at lower extent produced water-insoluble PVA fibrous membrane with least change to the interfiber porous structure. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3249-3255, 2010