Selective dehydration of glucose, the most abundant monosaccharide, was examined using a solid acid catalyst individually or a combination of solid acid and base catalysts to form anhydroglucose (levoglucosan) or 5-hydroxymethylfurfural (HMF), respectively. Glucose was dehydrated to anhydroglucose by acid catalysis in polar aprotic solvents including N,N-dimethylformamide. Amberlyst-15, a strongly acidic ion-exchange resin, functioned as an efficient solid acid catalyst for anhydroglucose production with high selectivity. In the presence of solid base, aldose ketose isomerization of glucose to fructose preferentially occurred by base catalysis, even in coexistence with the solid acid, resulting in successive dehydration of fructose to 5-hydroxymethylfurfural by acid catalysis with high yield in a one-pot reaction. A combination of Amberlyst-15 and hydrotalcite, an anionic layered clay, afforded high HMF selectivity under a moderate reaction temperature, owing to prevention of anhydroglucose formation. (C) 2010 Elsevier B.V. All rights reserved.