Antioxidant properties of the aqueous extracts of hulled barley (Hordeum vulgare L.) that had been roasted at 210 °C for 20 min were determined in bulk oil and oil-in-water (O/W) emulsions. Bulk oils were heated at 60, 100, and 180 °C, and O/W emulsions were oxidized under riboflavin photosensitization. The content of phenolic compounds was analyzed by high-performance liquid chromatography, and in vitro antioxidant assays were also conducted. The major phenolics contained in the aqueous extract of roasted hulled barley (AERB) were p-coumaric, ferulic, protocatechuic, chlorogenic, 4-hydroxybenzoic, and vanillic acids. Depending on the concentration and oxidation temperature, AERB had antioxidant or prooxidant properties in bulk oil. At 60 °C, AERB at a concentration of 0.5% acted as a prooxidant, whereas at 1.0% it acted as an antioxidant. At 100 °C, AERB acted as an antioxidant irrespective of concentration. In 180 °C conditions, 0.5% AERB acted as a prooxidant, whereas other concentrations of AERB acted as antioxidants. In the case of riboflavin photosensitized O/W emulsions, AERB showed antioxidant properties irrespective of concentration. Antioxidant abilities of AERB are affected by the food matrix, including bulk oil and O/W emulsions, and concentrations of AERB, even though diverse phenolic compounds may display high antioxidant properties in in vitro assays. Roasted barley has been widely used as a tea ingredient in East Asian countries such as Korea, China, and Japan. The highly antioxidative properties of the aqueous extracts of roasted barley have been confirmed in bulk oil and O/W emulsions as well as in vitro assays because of the presence of phenolic compounds. The results of this study can contribute to the development of antioxidant-rich beverages using roasted barley by aiding in the selection of proper food matrix-containing extracts of high phenolic compounds, as well as by expanding consumers’ choices for healthy beverages.