Aqueous biphasic systems (ABSs) composed of 1-alkyl-3-methylimidazolium tetrafluoroborate ([C(n)mim]BF4, n = 3 to 8) ionic liquids (ILs), 6-(hydroxymethyl)oxane-2,3,4,5-tetrol, and water for phenol extraction are reported in this work. The effects of the phase-forming components' concentrations, the temperature, the initial phenol concentration, and the length of the alkyl chain linked to the imidazolium ring on phenol partitioning behavior were investigated. The results showed that increasing the phase-forming components' concentrations, especially the glucose concentration, and the length of the alkyl chain linked to the imidazolium ring are quite favorable for phenol partitioning to the IL-rich phase. The distribution ratio (D) of phenol is as high as 78. The results are compared with previously reported work, and the effects on phenol extraction are explained from the point view of molecular structure and thermodynamic modeling.