Ionic liquids have been widely studied as effective reaction media for the conversion of glucose or cellulose to 5-hydroxymethhylfurfural (5-HMF). However, the recovery of 5-HMF from ionic liquids, typically carried out by extraction, has been encountered with very low extraction efficiency, which limited the reusability of the solvents. Through this work, based on the model biphasic system that consists of 1-butyl-3-methylimidazolium chloride ([BMIM] CO as the ionic liquid phase and methyl isobutyl ketone (MIBK) as the extractant phase, the dominant force that suppresses the extraction efficiency of 5-HMF was identified as being the strong hydrogen bonding between 5-HMF and [BMIM]Cl. Solvent mediation with functional promoters have been established as a new strategy to shift this force, resulting in improved extraction efficiency of 5-HMF from the ionic liquid. For example, with ethanol as a promoter, the distribution coefficient of 5-HMF was about 10 times higher than that without a promoter.