A steam explosion pretreatment process followed by methanol extraction has been applied for releasing and extracting phenolic compounds, as well as other effective components, from barley bran. The steam explosion treatment was performed at different temperatures ranging from 210 to 250 °C, with a residence time of 30 s. The effect of residence time was also studied in the range 10 s to 120 s at 220 °C. The extracts were evaluated for their total soluble phenolic content (TSPC) including total free phenolic acids (TFPC) and total soluble conjugates (TSC), identified phenolic acids, total antioxidant capacity (TAC), water-soluble carbohydrates (WSC) and total methanol extracts (TME). High-performance liquid chromatography (HPLC) coupled with a photodiode array detector (PDA) was used in this study for the analysis of p-coumaric acid and ferulic acid in barley bran before and after steam explosion. Our results indicate that TSPC and TAC increased with residence time. They also increased dramatically with temperature up to 220 °C. After steam explosion at 220 °C for 120 s, the TSPC reached 1686.4 gallic acid equivalents mg/100 g dry weight, which was about 9-fold higher than that of the untreated sample. The TSPC and TAC obtained were highly positively correlated (r = 0.918-0.993), which meant that the increase of TAC for the steam explosion pretreated barley bran extracts was due, at least in part, to the increase of TSPC in the methanol soluble fraction. Also, under optimum conditions, the WSC in aqueous solution was 5 times as much as that of the untreated sample, which demonstrated that steam explosion also hydrolyzes carbohydrates into water-soluble sugars. It can be concluded that a proper and reasonable steam explosion pretreatment could be applied to release the bound phenolic compounds and enhance the antioxidant capacity of barley bran extracts.