The objective of this study was to explore optimal extraction technology of β-glucan from bran of hull-less barley (Qingke in Chinese), and provide scientific basis for industrialization of β-glucan extraction from a commodity waste which is rich in β-glucan. β-Glucan extraction from bran of hull-less barley was performed with an accelerated solvent extraction (ASE) technique and compared with ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE), and reflux extraction. The best combination of extraction parameters was obtained through response surface methodology (RSM) with a three-variable-three-level Box-Behnken design (BBD). The optimum extraction parameters were as follow: extraction time for 9 min, extraction temperature at 70 °C, number of cycles at 4, and extraction pressure at 10 MPa. Under these conditions, the experimental extraction yield of β-glucan was 16.39 ± 0.3%, which agreed closely with the predicted value (16.33%). Compared with other extraction methods, ASE produced much higher β-glucan and more environmentally friendly extraction and solvent systems, less extraction discrimination and shorter time, and could be useful to the development of industrial extraction processes.