High-amylose maize refers to a special type of maize cultivar with a 50 %–90 % amylose content of the total starch. High-amylose maize starch (HAMS) is of interest because it possesses unique functionalities and provides many health benefits for humans. Therefore, many high-amylose maize varieties have been developed via mutation or transgenic breeding approaches. From the literature reviewed, the fine structure of HAMS is different from the waxy and normal corn starches, influencing its gelatinization, retrogradation, solubility, swelling power, freeze-thaw stability, transparency, pasting and rheological properties, and even in vitro digestion. HAMS has undergone physical, chemical, and enzymatical modifications to enhance its characteristics and thereby broaden its possible uses. HAMS has also been used for the benefit of increasing resistant starch levels in food products. This review summarizes the recent developments in our understanding of the extraction and chemical composition, structure, physicochemical properties, digestibility, modifications, and industrial applications of HAMS.