Barley (Hordeum vulgare L.) is mainly used as animal feed and in malting. In recent years, there has been growing interest in using barley for food production. Starch is the major component of the kernel and may amount up to over 70% of the dry weight. The quality of barley products is much determined by its starch properties such as gelatinization and retrogradation. Starch is also a by-product of the barley fractionation industry and can be utilized for value-added products. This review summarizes the recent developments in our understanding of the isolation, chemical composition, granular structure, chemical structure of starch components, physicochemical properties, and various modifications of barley starch. The structure-function relationships of starch are discussed. This review provides a basis for better utilizing barley starch, as well as the further development of barley as a sustainable crop.