In recent years, deep eutectic solvents (DESs) are used for enhancing the enzymatic digestibility and lignin fractionation in pretreatment, while hemicellulosic fraction receives scant attention. Herein, we report a novel approach of applying alkaline deep eutectic solvents (ADESs) for dissociating hemicelluloses from woody biomass. Among these ADESs, choline chloride-monoethanolamine (C-M) was the most efficacious medium for deconstructing the recalcitrant structure of poplar and 63.3% of hemicelluloses was obtained at 80 °C. Structure analysis showed that the ADESs-extracted hemicelluloses retained partial of O-acetyl groups. Different ADESs could be used to obtain hemicelluloses with various degrees of branching. Furthermore, the enzymatic digestibility of cellulose was significantly increased by 6.6 times compared to that of the untreated poplar under the optimum conditions (C-M, 140 °C). This work provides a view on the dissociation behavior of hemicelluloses during ADESs pretreatment, which would be beneficial for devising DESs toward effective fractionation and comprehensive utilization of biomass.