Many efforts to spin starch fibers are reported in the patent and research literature. All reported spinning methods are dependent upon addition of non-starch components, e. g. other polymers, plasticizers or cross-linkers. In the present study, we demonstrate a method of producing pure starch fibers by an electrospinning technique. This method involves choosing an appropriate solvent for native high amylose starch and spinning on a modified electrospinning setup. Resulting starch fibers have diameters in the order of microns. Coagulation solvent composition can affect the crystallinity of the starch fibers. Post-spinning treatments were employed to increase the crystallinity and cross-link the starch fibers. The novel starch fibers have potential in various applications, e. g. in the food, textile, and biomedical industries. (c) 2013 Elsevier Ltd. All rights reserved.