AbstractBiomass pretreatment by autohydrolysis uses hot-water to extract soluble components from wood prior to converting the woody residuals into paper, wood products, or fuel, etc. Mixed hardwood chips were autohydrolyzed in hot-water at 150, 160, 170, and 180 ºC, for 1 and 2 h. The tradeoff between fermentable sugar yield and caloric value of the residual solids was studied for a process that will be referred to as “value prior to combustion”. The extracted liquid was treated with dilute sulfuric acid to break down sugar oligomers into fermentable monomers. Material balances were performed around autohydrolysis to evaluate the role of temperature and residence time on sugar production and residual solid heating value. The composition (sugars and byproducts) of the extracted liquid was determined. As the autohydrolysis temperature increased, the material balance became less precise, presumably due to more volatile byproducts being formed that were not quantified. More hemicelluloses were extracted from the wood by the hot water extraction process under higher temperature and longer residence time, but a greater degree of sugar degradation was also observed. After hot-water extraction the heating value of the solid residues was higher than the original wood. The total energy content of the residual solid after extraction ranged from 74 to 95% of the original energy content of the feed.