The objective of this study was to investigate the structural and physicochemical properties of starch by barely cultivars. Hwanggeumchal had a moisture content and β-glucan content of 12.02 and 6.23%, respectively. Hyegang had higher protein contents than those of the other cultivars. As a result of observing the particle size of starch, Hwanggeumchal and Hyegang had smaller particles of starch compared with the other cultivars at 15.7 and 15.9 μm, respectively. The analysis results on the content of damaged starch showed that Dahan and Hyegang had a damaged starch content of 1.14 and 1.20%, whereas Boseokchal and Hwanggeumchal were 0.76 and 0.49% respectively, showing low waxy varieties. As for the content of amylose, the results show that Dahan and Hyegang had an amylose content of 37.07 and 37.75%, and Boseokchal and Hwanggeumchal were at 11.22 and 37.75%, respectively. As for the degree of amylopectin polymerization, all four varieties had the highest degree of polymerization (DP) content of 13-24 at more than 54%, whereas the DP content ≥ 37 was the lowest at less than 5.35%. The results for the soluble and resistant starch content show that the content of soluble starch ranged from 93.90 to 95.76%, and resistant starch was 0.17 - 0.40%. After analyzing the gelatinization properties of barley starch, the value of the setback was low in Hwanggeumchal and Hyegang; thus, it is considered that the aging process of those cultivars will be slower than that of the others.