DMSO can improve the selectivity of 5-hydroxymethylfurfural (HMF) in the conversion of carbohydrates. However, one of the bottlenecks in its application is product separation. Thus a one-pot synthesis of 5-ethoxymethylfurfural (EMF) rather than HMF from fructose in ethanol-DMSO was investigated. Phosphotungstic acid was used as an effective catalyst. The yield of EMF can be reached as high as 64% in the mixed solvent system of DMSO and ethanol within 130 min at 140 degrees C. Ethyl levulinate (LAE) was detected as the main by-product, the yield of which increased with the reaction time, temperature and the amount of catalyst. In addition, the existence of water could significantly reduce the yield of EMF and increased the yield of LAE. Most importantly, it was discovered that EMF could be much more efficiently extracted from the reaction solvent system by some organic solvents than HMF. (C) 2013 Elsevier Ltd. All rights reserved.