AbstractExtraction of hemicelluloses from wood prior to pulping is being pursued to generate more value-added products, while still producing high quality pulp from the pre-extracted wood. For a better understanding of the factors limiting selective extraction, enzymatic hydrolysis in combination with size exclusion chromatography (SEC) was applied to milled wood and hydrothermally treated wood. Complete dissolution was achieved in a lithium chloride/dimethylacetamide solvent system after mild ball-milling of a Southern Hardwood Mixture (SHM), of SHM extracted using auto-hydrolysis, and of enzyme-treated SHM. SEC tests showed that severe degradation of wood polymers occurred after a milling time of 3 hours. The SEC data also confirmed the presence of lignin-carbohydrate complexes. Based on the results, it is suggested that linkages between lignin and polysaccharides may play an important role in limiting extraction of hemicelluloses.