Although high‐amylose starches are not a recent innovation, their popularity in recent years has been increasing due to their unique functional properties and enhanced nutritional values in food applications. While high‐amylose maize, barley, and potato are commercially available, high‐amylose variants of other main crops such as wheat and rice have once been developed more recently and will be available commercially in the near future. This review summarizes the development, structure, and nutritional functionality of high‐amylose starches developed and reported so far. The range of biotechnological strategies utilized are reviewed, as are the consequent effects on structural properties at different length scales, as well as sensory aspects of foods containing high‐amylose starch (HAS). This review identifies the molecular and microstructural features contributing to digestive enzyme resistance not only in native HAS but also in forms of relevance to food processing. During heat treatment, HAS tends to retain or form dense molecular structures that resist amylase degradation through the retention of the granular structure as well as helices (type‐2 resistant starch [RS]), reassociation of glucan chains (type‐3 RS), and formation of lipid–amylose complexes (type‐5 RS). The review also identifies opportunities for food manufacturers and consumers to incorporate HAS in food products and diets for better nutritional outcomes.

Background: Starch is a complex branched glucose polymer, mainly comprising amylose and amylopectin. The number of individual chains as a function of the number of monomer units they contain, i.e. the chain-length distributions (CLDs), are controlled by the underlying biosynthetic process occurring during plant growth. CLDs are currently commonly related to biosynthetic processes and to functional properties by dividing into arbitrarily chosen regions.