We examine single step reactive electrospinning of poly(vinyl alcohol) (PVA) and a chemical cross-linking agent, glutaraldehyde (GA), with hydrochloric acid (HCl) as a catalyst to generate water insoluble PVA nanofibers. Such ail approach using a conventional setup with no modification enables the fibers to cross-link during the electrospinning process, thereby eliminating the need for post-treatment. Significant changes in the rheological properties Occur during in situ cross-linking, which we correlate with electrospinnability. In particular, we associate changes in dynamic rheological properties to changes ill fiber morphology for two regions: (1) below the critical concentration to electrospin PVA only and (2) above the critical concentration to electrospin PVA only. In region I fiber morphology changes from beaded fibers to uniform fibers to flat fibers, and in region 2 fiber morphology changes from uniform fibers to flat fibers. Electrospinning windows to generate uniform fibers for both regions are determined and can be manipulated by changing the molar ratio of GA to PVA and the volume ratio of HCl to GA. The electrospun fibrous material generated can be rendered insoluble in water, and the uniform fiber morphology can be maintained after soaking ill water overnight. I-lie reactive electrospinning process also lowers the critical PVA concentration required for successful electrospinning of the system.