Starch, a natural glucan polymer, exhibits a complex hierarchical structure. Acquiring a comprehensive understanding of the self-assembly of glucan polymers in starch granules has been of significant interest for many decades, due not only to their structural complexity but also to their dietary importance and widespread applicability in the food and nonfood sectors. The primary focus of this article is the organization of glucan chains at different structural levels of the starch granule, with particular emphasis on the molecular structure of the amylopectin, which forms the unique architecture of the starch granule.