This work deals with the effective fractionation of bioactive ketoses, i.e. lactulose and tagatose, from their corresponding aldoses, lactose and galactose, in equimolar binary mixtures driven by room temperature ionic liquids, i.e. 1-ethyl-3-methylimidazolium dicyanamide ([EMIM][DCA]) and 1-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO4]), respectively. Under assayed conditions, tagatose was found to be 6-fold more soluble on [BMIM][MeSO4] than galactose; meanwhile lactulose was 3 times more soluble than lactose on [EMIM][DCA]. As an application example in a more complex sample, a lactose isomerization mixture containing in addition lactulose and monosaccharides was enriched in this ketose by using [EMIM][DCA]. Carbohydrates were then successfully recovered from the ionic liquid following an activated charcoal-based treatment. Overall, lactulose content was enriched from a 24% in the initial isomerization reaction mixture to a 62% in the purified sample. These experimental results demonstrated the potential of ionic liquids as green alternative solvents for the selective fractionation of bioactive ketoses from their corresponding aldoses in food and beverage production. (C) 2015 Elsevier B.V. All rights reserved.