Wood and wood materials are highly sensitive to moisture in the environment. To a large extent this relates to the hygroscopicity of wood hemicelluloses. In order to increase our understanding of the effects of moisture sorption of the major wood hemicelluloses, glucomannan and xylan, model experiments using films of amorphous konjak glucomannan and rye arabinoxylan were conducted. Moisture-induced expansion and stiffness softening were characterized using dynamic mechanical testing. Both hemicelluloses showed a threshold around 5Â % of moisture content above which swelling increased whereas the modulus decreased by more than 70Â %. FTIR spectra, using H2O and D2O, indicated that even at high RH about 15Â % of the hydroxyl groups were not accessible to hydrogen exchange by D2O. For xylan both hydroxyl groups were found to exchange in the same manner while for the glucomannan the O(6)H group seemed to be the most accessible.