Response surface methodology was used to predict optimum conditions for hot air roasting of barley grains (temperature, time, and amount). Antioxidant capacity in the grains was highest under optimum conditions of 250 °C, 63.5 min and 42 g (one and a half layers). A correlation of R 2 = 0.74 (p < 0.05) was found between 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activity and total phenolic contents. Ethanol and aqueous extracts were prepared from grains roasted under optimum conditions and assessed for antioxidant capacity. Antioxidative compounds in the extracts were then identified using GC–MS. The IC50 value of ethanol extract was significantly lower (11.45 μg mL–1) than that of aqueous extract (33.54 μg mL–1) and α-tocopherol (12.6 μg mL–1) but higher than BHT (9.59 μg mL–1). The same trend was observed in linoleic acid assay. In reducing power, the ethanol extract and α-tocopherol were not significantly different. Phenolic acids p-hydroxybenzaldehyde, vallinic and gallic acids were identified as the major compounds in the extracts. The results obtained from this study show that it is possible to optimize antioxidant capacity in barley grains during roasting.