The wide molar mass distribution of native starch creates obstacles in investigating the physicochemical characteristics of starch, such as retrogradation, because samples thought to be the same are actually compounds containing many chains with different molar masses. In this paper, the sweet potato amylose and amylopectin isolated from retrograded starch were treated with the retrogradation–hydrolysis method three times, and their physicochemical changes in this process were determined by absorbance of the starch–iodine complex, light microscopy, and molar mass and chain length distributions. The results showed that repeated retrogradation and hydrolysis caused the molar mass distribution of sweet potato amylose and amylopectin to reduce from 4.2 × 107–205 and 7971–223 to 6.0 × 104–730 and 4533–211 g mol−1, respectively. This retrogradation–hydrolysis cut the chain length distribution of sweet potato amylose from DP 9–35 to DP 3–13, but that of amylopectin remained unchanged. The double helix in sweet potato amylopectin will not form if the percentage of chain length with DP ≥ 4 is less than 25%. Repeated retrogradation and hydrolysis was an appropriate method to obtain amylose or amylopectin with a narrower molar mass distribution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43849.