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Though the retrogradation property as affected by starch fine molecular structures has been widely investigated, it remains largely unexplored how concurrent starch structures and storage conditions e.g. temperature tailor the starch retrogradation property. The amylopectin long-term retrogradation for 8 different rice starches with a broad range of amylose content was thus investigated under different storage temperatures. Results showed that gelatinized starch stored at −20 °C generally had a narrower melting temperature range from differential scanning calorimetry, while larger cells and thicker cell walls in the gel matrix than that stored at 4 °C. Different linear correlations were found between starch fine molecular structures and amylopectin retrogradation parameters when starch was stored under different temperatures. For example, the melting enthalpy of retrograded starch double helices was negatively correlated with the amount of amylose intermediate chains at 4 °C, while positively correlated with the relative length of amylopectin short chains at −20 °C. Under both temperatures, rice starch R250 had the highest retrogradation enthalpy. These results could help the rice industry improve both the nutritional and textural attributes of cooked rice by selecting starch with desirable molecular structures and optimizing the storage conditions for rice after cooking. [ABSTRACT FROM AUTHOR]