Steam explosion pretreatment was used to release hemicelluloses from the stalks of Lespedeza crytobotrya, a potential woody biomass crop. Hemicelluloses from Lespedeza crytobotrya subjected to five different pretreatment severities were extracted with 60% aqueous ethanol solution containing 1% NaOH, characterized by component analysis, gel permeation chromatography (GPC), FT-IR, NMR spectroscopy, and thermal analysis, and compared with hemicelluloses obtained from untreated stalks. It was found that the hemicellulosic fractions mainly consisted of arabinoxylans and β-glucans or xyloglucans. Steam explosion pretreatment yielded noticeable degradation and debranching reactions, illustrated by a linear decrease of molecular weight and Ara/Xyl ratio with increasing severity. For further high-value utilization of the hemicellulosic polymers, steam explosion at 20 or 22.5 kg/m2 for 4 min is promising because of improved extraction efficiency and avoidance of over-drastic degradation of the polymers.