It has often been claimed that the equilibrium moisture content (EMC) of wood is controlled by the available hydroxyl group content and their accessibility, but this has not been proven. In the present study, the accessibility of the hydroxyl groups were analysed by deuterium exchange in a dynamic vapour sorption apparatus, and generally poor correlation with the EMC and hydroxyl group accessibility was found. Therefore, the role of the accessibility of wood hydroxyl groups in relation to exerting sole influence on the EMC is disputable. It is concluded that there has to be an additional mechanism to exercise control over the EMC in addition to hydroxyl group accessibility.