The formation of starch-polyphenol complexes through high-pressure homogenization (HPH) is a promising method to reduce starch digestibility and control postprandial glycemic responses. This study investigated the combined effect of pH (5, 7, 9) and polyphenol structures (gallic acid, ferulic acid, quercetin, and tannic acid) on the formation, muti-scale structure, physicochemical properties, and digestibility of pea starch (PS)-polyphenol complexes prepared by HPH. Results revealed that reducing pH from 9 to 5 significantly strengthened the noncovalent binding between polyphenols and PS, achieving a maximum complex index of 13.89 %. This led to the formation of complexes with higher crystallinity and denser structures, promoting a robust network postgelatinization with superior viscoelastic and thermal properties. These complexes showed increased resistance to enzymatic digestion, with the content of resistant starch increasing from 28.66 % to 42.00 %, rapidly digestible starch decreasing from 42.82 % to 21.88 %, and slowly digestible starch reducing from 71.34 % to 58.00 %. Gallic acid formed the strongest hydrogen bonds with PS, especially at pH 5, leading to the highest enzymatic resistance in PS-gallic acid complexes, with the content of resistant starch of 42.00 %, rapidly digestible starch of 23.35 % and slowly digestible starch of 58.00 %, and starch digestion rates at two digestive stages of 1.82 x 10(-2) min(-1) and 0.34 x 10(-2) min(-1). These insights advance our understanding of starchpolyphenol interactions and support the development of functional food products to improve metabolic health by mitigating rapid glucose release.
