Sugar alcohols, such as xylitol, sorbitol and inositols, are added-value carbohydrates with relevant bioactive and technological properties. These features make their extraction from natural sources of great interest both from the scientific and industrial points of view. However, due to the similarity of the chemical structures of the different carbohydrates and the complexity of the extracted mixtures, the subsequent isolation of these sugar alcohols from other coextracted low molecular weight carbohydrates (LMWC) is still considered a challenging task. In this article, the solubility of linear sugar alcohols and inositols in selected ionic liquids (ILs), i.e., 1-hexyl-3-methylimidazolium chloride ([HMIM][Cl]), 1-ethyl-3-methylimidazolium dicyanamide ([EMIM][DCA]), 1-ethyl-3-methylimidazolium acetate ([EMIM] [OAc]) and 1,3-dimethylimidazolium dimethylphosphate ([MMIM] [Me2PO4]), has been investigated. The experimental results demonstrated widely divergent solubilities (in the 1.7-84.7%, w/w, range) for the several targeted carbohydrates in the different ILs evaluated, with [EMIM] [OAc] and [MMIM][Me2PO4] providing the highest solubility values. These Its gave also the best results when applied to the selective fractionation of sugar alcohols from other LMWC in 1:1 (w/w) binary mixtures (yields in the 60-98% range). These results show Its as promising non-volatile and environmental friendly solvents for this type of fractionation process and suggest the interest of further investigation in this particular application field.