Influencing the starch postprandial glycemia via interventions that are sourced from natural plant materials has gained attention recently. Amylose present in starch is reported to form complexes with small ligands such as gallic acid (GA) through a conformational change that are digested slowly and contribute to the formation of resistant starch. In this study, the molecular interactions, multi-scale structure and in vitro digestion properties of normal neat rice starch and rice starch-GA composites (2, 5 % w/v) obtained either by high hydrostatic pressure (HHP) or thermal (T) treatment were compared. The multi-scale structure changes experienced by the rice starch gels (neat and composite) during simulated oro-gastrointestinal (OGIT) digestion were also characterised. Overall, formation of the V