Barley flour is widely utilized in food and nonfood industries. Morphological, structural, and functional properties of starches extracted from waxy and non-waxy barley are investigated and compared in this work. The morphology of starch granules in waxy and non-waxy barley is similar while waxy barley has a higher proportion of A-type starch granules and a lower proportion of B-type starch granules than those of non-waxy barley. Compared with non-waxy barley starch, waxy barley starch shows higher amylopectin content with higher levels of amylopectin short and long branch-chains; better ordered structures with higher relative crystallinity, IR ratio of 1045/1022 cm −1 , and a double helical component, a lower amorphous and V-type single helix components. The gelatinization temperature and enthalpy of waxy barley starch are higher than those of non-waxy barley starch. Meanwhile, waxy barley starch presents higher swelling power, solubility, pasting viscosities, breakdown value, and lower setback value than those of non-waxy barley starch. Furthermore, waxy barley starch is more susceptible to acid and enzymatic hydrolysis than non-waxy barley starch. Results indicate that waxy and non-waxy barley starches differ in physicochemical properties, and waxy barley may have a better mouthfeel and edible quality.