<p>Hydrophilic starch-based nanofiber membranes are known to swell in water and have low tensile strengths, which makes them unsuitable for use as drug carriers in medical dressings. To address this issue, hydrophobic polymers—poly(hydroxyethyl acrylate) (PHEA), poly(hydroxypropyl acrylate) (PHPA), and poly(hydroxybutyl acrylate) (PHBA)—were grafted onto high amylose corn starch (HAS) at similar grafting ratios. Subsequently, electrospun membranes loaded with aspirin (AS) were produced and cross-linked using glutaraldehyde (GD) vapor for varying durations. The properties of these membranes, which included porosity, tensile strength, swelling capacity, water vapor transmission rate (WVTR), water contact angle (WCA), and cumulative release rate (CRR), were thoroughly examined. The results indicated that the combination of grafting and cross-linking significantly impacted these properties by enhancing hydrophobic interactions, van der Waals forces, and hydrogen bonds between HAS and AS through the introduction of hydrophobic branches, as well as through the creation of a three-dimensional structure. After grafting the branches from PHEA to PHBA, improvements were observed in the membrane’s anti-swelling properties, WCA, and controlled release of AS, while porosity and WVTR were reduced. As the cross-linking time increased, the membrane’s porosity, swelling capacity, WVTR, and CRR decreased gradually, whereas tensile strength and WCA increased. After the modification, the membrane samples still showed superior blood compatibility. Ultimately, the cross-linked HAS-<i>g</i>-PHBA membrane (cross-linking for 12&#xa0;h) was recommended as an effective AS carrier, supporting sustained release in starch-based medical dressings.</p> Graphical abstract <p></p>