Fully (99+ %) hydrolyzed poly(vinyl alcohol) (PVA) was electrospun from water using Triton X-100 surfactant to lower the surface tension. The diameter of the electrospun PVA fibers ranged from 100 to 700 nm. Treatment of the PVA fiber mats with methanol for 8 h stabilized the fibers against disintegration in contact with water. In addition, the mats showed increased mechanical strength due to increased crystallinity following post-spinning treatment with methanol. We suggest that methanol treatment serves to increase the degree of crystallinity, and hence the number of physical cross-links in the electrospun PVA fibers. This may occur by removal of residual water within the fibers by the alcohol, allowing PVA-water hydrogen bonding to be replaced by intermolecular polymer hydrogen bonding resulting in additional crystallization. Potential applications of electrospun PVA include filters, precursors to graphitic fibers, and biomedical materials.