Hydrogen sulfate ionic liquid as co-solvent and as homogeneous catalyst in ethanol solvent allows efficient conversion of fructose into 5-ethoxymethylfurfural (5-EMF) directly at mild conditions. Ionic liquids [A][B] ([A](+) = 1-methylimidazolium, [C(1)im](+); 1-ethyl-3-methylimidazolium, [C(2)mim](+); or 1-butyl-3methylimidazolium, [C(4)mim](+), [B](-) = hydrogen sulfate, [HSO4](-); acetate, [AC](-); diethylphosphate, [DEIT](-)); dimethylphosphate, [DMP](-)) or chloride, [Cl](-) were studied. In the [C(4)mim][HSO4]-ethanol system, 83% 5-EMF yields were obtained from fructose at 130 degrees C in 20 min reaction time that can be attributed to the anion acidity and to a stabilizing hydrogen bond that forms between the ionic liquid and 5-HMF. The ionic liquid was demonstrated to be reusable for five times with minimal loss in catalytic activity (ca. 3% loss in 5-EMF yield). Hydrogen sulfate ionic liquids as co-solvent and catalyst in ethanol allow efficient conversion of biomass-related mixtures that contain fructose or a 5-HMF intermediate into biofuels.(C) 2016 Elsevier B.V. All rights reserved.