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This chapter discusses formations of resistant starch (RS) and elongated starch granules in the maize ae‐mutant starch and how the effect of high‐amylose modifier (HAM) gene on the RS content of the maize ae‐mutant starch. The structures and properties of the high‐amylose maize starch and its RS residue have been intensively studied in order to understand the RS formation in the starch. It has been reported that molecular weight and branch chain length distributions of RS residues remaining after pancreatic α‐amylase hydrolysis are similar to that of native starch counterparts. Starch granule formation in the amyloplast of high‐amylose maize endosperm at an early stage of kernel development (20 DAP) has been studied using transmission electron microscopy (TEM). Long‐chain double‐helical crystallites of amylose/IC in high‐amylose maize starch are developed during kernel development and are …