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This paper evaluated the relationship between multi-scale structure and high-pressure gelation properties of nine types of starches with different amylose (AM) content and crystalline polymorphic structure by RVA 4800. Higher average chain lengths of long amylopectin (AP) chains (DP 36) and AM content, and lower relative content of short AP chains (DP ≤ 36) contributed to the higher peak temperature and peak time at 95-140 °C, and lower peak viscosity, through viscosity, and final viscosity at 95-110 °C. Rheological and texture pa