We performed a dual-modification of starch via debranching and graft copolymerization to improve its adhesion to fibers. We synthesized the partly debranched starch-g-poly(2-acryloyloxyethyl trimethyl ammonium chloride) (PDS-g-PATAC) using horseradish peroxidase in the presence of hydrogen peroxide and acetylacetone. PDSs of different molecular structures were prepared by debranching waxy cornstarch for different periods of time. With increasing debranching time, the degree of hydrolysis of PDS increased from 0.85 % (10 min) to 1.13 % (30 min), while the degree of branching decreased from 8.37 % to 7.99 %. Fourier transform infrared analysis confirmed that ATAC units had been successfully grafted onto the starch (debranched or not debranched). The degree of substitution (DS) and grafting ratio (GR) of the PDS-g-PATACs were characterized by H-1 nuclear magnetic resonance. The DS and GR of grafted starches positively related with debranching time. Thermogravimetry-differential thermogravimetry analysis showed that grafted starch had lower thermal stability than ungrafted starch. The adhesion of PDS-g-PATAC to polyester/cotton yarns was evaluated. The PATAC chains grafted onto the starch enhanced the adhesion of starch to polyester/cotton yarn. The grafted starch produced from the copolymerization of PDS (after debranching for 10 min), exhibited the strongest adhesion to polyester/cotton yarn with a resulting tensile strength of 98.20 N.