Converting hemicellulose into valuable platform chemicals is a key step in developing an integrated biorefinery. Traditionally, hemicellulose conversion into xylitol is done in two steps, using mineral acids and enzymes. Here we report a one-pot hydrolysis–hydrogenation of hemicellulose to xylitol. We used a combination of either heteropoly acid or biomass-derived organic acid and Ru on carbon as catalyst. Silicotungstic acid, phosphotungstic acid, and lactic acid can be used efficiently in the hydrolysis part. Phosphomolybdic acid was not very active (