The effect of organosolv pretreatment was investigated using a 30 L bench-scale ball mill reactor that was capable of simultaneously performing physical and chemical pretreatment. Various reaction conditions were tried in order to discover the optimal conditions for the minimal cellulose loss and enhanced enzymatic digestibility of Miscanthus × giganteus (MG), with conditions varying from room temperature to 170 °C for reaction temperature, from 30 to 120 min of reaction time, from 30% to 60% ethanol concentration, and a liquid/solid ratio (L/S) of 10–20 under non-catalyst conditions. The pretreatment effects were evaluated by chemical compositional analysis, enzymatic digestibility test and X-ray diffraction of the treated samples. The pretreatment conditions for the highest glucan digestibility yield were determined as 170 °C, reaction time of 90 min, ethanol concentration of 40% and L/S = 10. With these pretreatment conditions, the XMG (xylan + mannan + galactan) fractionation yield and delignification were 84.4% and 53.2%, respectively. The glucan digestibility of treated MG after the aforementioned pretreatment conditions was 86.0% with 15 filter paper units (FPU) of cellulase (Cellic® CTec2) per g-glucan enzyme loading.