Barley and its products are good sources of antioxidants. This experiment was conducted to examine the classification and concentration of phenolic compounds, proanthocyanidins, and anthocyanins in 127 lines of colored barley. Their relationship with 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity was also examined. Barley was placed into seven groups using the colorimeter: hulled (black 1, black 2, black 3, and purple) and unhulled (black, blue, and purple). The contents of phenolic compounds and anthocyanins were analyzed by using HPLC. The average content of phenolic compounds in unhulled barley groups (268.6 microg/g) was higher than that in hulled (207.0 microg/g) (P > 0.05). The proanthocyanidins content was determined by modified vanillin assay. The average content of proanthocyanidins was significantly higher in purple and blue barley groups compared with black (P < 0.05). The content of anthocyanins varied from 13.0 to 1037.8 microg/g. Purple and blue barley groups contained higher average contents of anthocyanins than black (P < 0.05). The most common anthocyanin in the purple barley groups was cyanidin 3-glucoside, whereas delphinidin 3-glucoside was the most abundant anthocyanin in the blue and black groups. In colored barley, DPPH radical scavenging activity had high positive correlation to the content of phenolic compounds and proanthocyanidins.