Electrospinning encapsulation is a highly viable method to protect bioactive compounds and prevent their degradation. Hence, this study produced ultrafine fibers based on yellow and white sweet potato starches and a red onion skin extract (ROSE; 0, 3, 6, and 9 %, w/w) using electrospinning. The fibers were evaluated for morphology, thermogravimetric properties, antioxidant, in vitro release simulation, thermal resistance (100 and 180 °C), and wettability. The fibers with ROSE presented 251–611 nm diameters, 67–78 % loading capacity, and 51.6–95.4 and 13.4–99.4 % thermal resistance (100 and 180 °C, respectively); apigenin presented the highest thermal protection. The phenolic compounds showed low release using 10 % ethanol and greater release with 50 % ethanol. The fibers with 9 % ROSE showed 2,2′-azino-bis(3-ethylbenzothiazoline) 6-sulfonic acid radical inhibition above 92 %. The ultrafine fibers and the unencapsulated ROSE showed inhibitory action against Escherichia coli and Staphylococcus aureus; only unencapsulated ROSE showed bactericidal activity.