Aspen wood was treated with steam at different time-temperature severity factors. Analysis of the amounts of acids released revealed a relationship between the acidity and the formation of furfural and hydroxymethyl furfural as degradation products from carbohydrates. It is suggested that two concurrent or consecutive mechanisms are responsible for the observed results: a homolytic cleavage and an acid hydrolysis of glucosidic linkages in the polysaccharides. By preimpregnating the wood with alkali, hydrolysis can be eliminated, resulting in a much cleaner depolymerization of the polysaccharides without any further acid-catalyzed degradation. The enzymatic digestibility of the steam-treated wood material for the formation of glucose was compared with that of steam-exploded wood. A more efficient route for glucose production from steam-exploded wood was found as long as the biomass-pretreated material was homogeneous and without shives.