Phenolic compounds, which are important substances in industry, are mainly derived from coal liquefaction oil, coal tar, and petroleum, and also from biomass via pyrolysis. However, the traditional process of separation of phenols from oil using water, NaOH, and H2SO4 causes serious environmental problems. In this work, imidazolium-based ionic liquids (ILs) were used to extract phenol from a model oil of hexane and phenol in order to reduce environmental risk It was found that these ILs could successfully separate phenols from hexane, and a small amount of [Bmim]Cl, equimolar to that of phenol in hexane, was enough to extract phenol with a high extraction efficiency of 99%. Anions of imidazolium-based ILs have a significant influence on the phenol extraction efficiency, which follows the order: Cl- > Br- > BF4- > PF6-. But the cation of these ILs shows a relatively small influence on the extraction. Particularly, [Bmim]Cl shows best performance in terms of phenol extraction efficiency. Furthermore, it is not sensitive to temperature changes and can be performed at ambient temperature. The extracted phenol in ILs could be recovered by evaporation, and the regenerated ILs could be reused for four cycles with no obvious loss in the phenol extraction efficiency. [Bmim]Cl was also used to extract phenols from real coal liquefaction oil, and the extraction efficiency of phenols could reach 90%.