The main objective of the present work is the investigation of a new method for starch hydrolysis. For this, we proposed the acid hydrolysis under the action of an external electric field, able to develop a faster reaction than the conventional one. Corn starch with 18% amylose was subjected to a fixed voltage, varying the external electric field application time and the number of cycles. Morphology, crystallinity, and thermal stability of the starches were investigated by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), and small-angle X-ray scattering (SAXS). The results showed that the acid hydrolysis coupled with an external electric field allows a significant reduction in hydrolysis time, due to the orientation of the electrolyte ions. Cavities were observed at the surface of hydrolyzed starches after treatment. However, the principal feature is related to the increase of the granule crystallinity with increasing hydrolysis time. The results suggest that the starches treated by this new method are interesting candidates for application in the food industry if greater gelatinization resistance is required.