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Starch‐based materials have received great attention for textile warp sizing due to their high modification potentiality, low cost, and biodegradability. However, the brittleness of starch film and low compatibility with polyester has made it challenging to withstand the friction of modern high‐speed weaving machinery. To overcome such drawbacks, a series of irradiated‐cornstarch acetate‐g‐poly (acrylic acid‐co‐2‐hydroxyethyl acrylate) samples with different grafting ratios were designed and prepared in this study. Fourier transform infrared, X‐ray diffraction, and scanning electron microscopy were employed to characterize the structural properties. The prepared starches were cooked for sizing on the roving and spun yarn, for the film formation. The adhesion was evaluated by measuring the bonding force of starch to roving fibers, the abrasion resistance of sized polyester yarn, and water dispersion. Whereas the film properties were investigated in terms of tensile strength, elongation, hydrophilicity, and moisture regain from the air. Results revealed that esterification‐grafting can significantly improve adhesion and film mechanical properties. The enhancement of abrasion resistance reached to 262%. With the increase of grafting ratio, hydratability, water dispersion, and elongation of the film increased, twice as high as that of irradiated‐cornstarch (IS). Desizability was above 88%, reaching the industry standard. The improvement in the warp sizing performance demonstrated that combining acetylation with hydrophilic branches is an effective strategy for the development of high‐performance starch sizing materials.