Barley is rich in nutritionally positive compounds, but the quality of bread made of wheat–barley composite flours is impaired when a high percentage of barley is used in the mixture. A number of enzymes have been reported to be useful additives in breadmaking. However, the effect of β-glucanase on breadmaking has scarcely been investigated. In this paper, the influence of different levels (0.02, 0.04, 0.06, and 0.08%, based on composite flour) of β-glucanase (100,000 U/g) on the properties of dough and bread from 70% wheat, 30% barley composite flour were studied. Although dough development time, dough stability, and protein weakening value decreased after β-glucanase addition, dough properties such as softness and elasticity as well as bread microstructure were improved compared with the control dough. β-Glucanase also significantly improved the volume, texture, and shelf life of wheat–barley composite breads. The use of an optimal enzyme concentration (0.04%) increased specific volume (57.5%) and springiness (21%), and it reduced crumb firmness (74%) and staling rate. Bread with added β-glucanase had a better taste, softness, and overall acceptability of sensory characteristics compared with the control bread. Moreover, the quality of wheat–barley composite bread after addition of 0.04% β-glucanase was nearly equal to the quality of pure wheat bread. These results indicate that dough rheological characteristics and bread quality of wheat–barley composite flour can be improved by adding a distinct level of β-glucanase.