Ruijuan Kang, Tabitha Halliday, James Railton, Maria Benlloch‐Tinoco
• Green tea phenolics predominantly formed non-inclusion interactions with amylose. • The rice starch network was reinforced by complexation with the green tea extract. • Complexation with green tea extract improved the storage stability of rice starch. • Rice amylose played a key role in the green tea phenolic’s effect on gel structure. Interactions between starch and dietary polyphenols are increasingly investigated to modulate starch digestibility and enhance functional performance in food systems. This study explores the impact of complexation between green tea polyphenols (GTE) and rice starch on digestibility, multi-scale structure, and storage stability of normal (NRS) and waxy (WRS) systems (15% w/v). Normal and waxy starch gels and starch–GTE composites (2%, 5% w/v) were gelatinised (90°C, 20 min), cooled and stored at 4°C for up to 14 days or subjected to three freeze–thaw cycles. Multi-scale characterisation was performed using FTIR, XRD, texture analysis profile, light microscopy and rheology. Additionally, the in vitro digestibility and syneresis of these samples were evaluated. FTIR and XRD data confirmed complexation via both inclusion (V 6 -type) and non-inclusion intermolecular hydrogen bonds in the composite samples. The NRS–GTE (5% w/v) composites were significantly less digestible (C ∞ ∼64 mg∙100g −1 ) and adhesive (67 g∙s −1 ) than the NRS sample, showing improved storage stability under refrigeration and freezing conditions (p<0.05). These effects were attributed to starch-GTE interactions that reinforced the gel network while partially hindering amylose reassociation, which was influenced by amylose content and the GTE extract miscibility within the matrix. Our findings provide new insight into the complexation-digestibility-structure relationship of rice starch and dietary polyphenols mixtures, offering a basis for reformulating palatable, ready-to-eat rice-based foods with tailored digestibility and enhanced storage stability.