Starch phosphate content (SPC) is an important structural parameter affecting the functionality of tuber starches, but how different phosphate groups affect starch structures is still unknown. In this study, four potato starches with different SPC were selected as models to investigate the effects of SPC on their multi-scale structures. A higher SPC is related to more long amylopectin (AP) chains with a degree of polymerization (DP) >24, fewer short AP chains with DP