Starch, an abundant carbohydrate polymer, naturally exists in granular form and serves as a common clean-label food additive. However, its native structure limits its application. We explored the application of electrospinning techniques for starch modification aimed at improving its functionality, particularly the thickening ability and emulsifying properties. Through electrospinning, large starch granules were converted to thin fibers, and were further tailored to rod-shape particles with different aspect ratios. These modified materials exhibited ~106-time increase in viscosity compared to unmodified starch owing to the rod-rod interaction and high surface area in contrast to the conventional gelatinization-based mechanism. These tailored particles hold the potential to serve as superthickeners in future foods with low calories. In addition, we found that the tailored particles acted as emulsifier by adsorbing onto oil-water interface owing to a more effective surface coverage. We further advanced our study by co-electrospinning starch with whey protein and plant-based proteins. The resulting fibrous emulsifier exhibited superior performance compared to starch rods developed previously, which already demonstrated enhanced emulsifying properties compared to native starch. Moreover, we addressed the challenge of electrospinning limited to high amylose content starch through enzymatic debranching. Results showed improved electrospinnability of starch from various botanical sources after debranching. This research not only filled a gap in the field by utilizing electrospinning techniques to modify the morphologies and characteristics of starch, enhancing its functionalities, but also expanded the applicability of electrospinning technique to various starch types, eliminating the limit to starches with high amylose content.