Multi-scale structures were investigated to understand starch digestibility of instant rice. A wide range of maximum starch digested ratio, up to about 20%, was observed among instant rice prepared from different rice varieties. Instant rice with a smooth and densely packed cross-section showed slower starch digestibility than those with a porous and loosely packed structure. All samples displayed B + V type crystallinity, with V-type crystallinity negatively correlating with maximum starch digested percentage. After digestion, starch chain-length distributions were significantly altered: rapidly digested starch comprised long amylose and short amylopectin chains, while slowly digested starch comprised chains with a peak degree of polymerization (DP) around 130. These results indicate that instant rice with a compact microstructure, high V-type crystallinity, and DP 130 fractions during digestion can reduce starch digestibility. This study provides insights for food industry to develop instant rice products with slow starch digestibility, potentially improving human health.