AbstractStarch can be modified by chemical and physical methods. In this study, electrolysis of barley flour (>99% amylopectin) suspension (1:6 w/w in water) is investigated to understand the effect of electrical voltage (5–30 V) and platinum electrode length (4–8 cm) on the structural properties of barley starch isolates, its aerogels, and hydrogels made in the presence of rutin. After 30 min of electrolysis treatment, the isolated starches have higher magnesium (2.9%) and phosphorus(13.0%) contents compared to 0.8% and 3.5% of the alkali‐treated starch, respectively. The Fourier Transform Infrared analysis shows that electrolysis enhances starch crystallinity, which is reduced by rutin. Also, high water absorption capacity (1659 ± 24%) is observed for electrolyzed starch (15 V/8 cm) aerogels but is reduced by the addition of rutin to 566 ± 70%. All electrolyzed starch hydrogels are opaque and firm (25 g) after 40 days at 23 °C. Green electrolysis process offers chemical (metal complexation) and physical (crystallinity) modification for barley starch.