Abstract: The main components in the 100−220 ℃ fraction of direct coal liquefaction oils are phenolic compounds, aromatic hydrocarbons and aliphatic hydrocarbons, in which their mass content percentages are 35.50%, 35.25%, and 28.17% respectively. In order to decrease the hydrogen consumption in the downstream processing, the best way is to extract the phenolic compounds firstly. The authors employed the conductor-like screening model for real solvents (COSMO-RS) model to screen the deep eutectic solvents (DESs) for phenol-aromatic hydrocarbon system, and applied the σ-profile and σ-potential to study the interactions of DESs with the phenols, aromatics, and aliphatic hydrocarbons to be separated during the extraction process; With the help of Infrared spectroscopy and Ultraviolet-visible spectroscopy, the mechanism of phenol extraction by DESs was revealed; Three types of DESs with different mass ratios will be screened: Sample 1 is Choline Chloride (ChCl)∶Ethylene Glycol (EG) (1.0∶1.5), Sample 2 is Betaine (Bet)∶EG (1.0∶2.5), Sample 3 is Tetraethylammonium Bromide (TEAB)∶EG (1.0∶3.0), were used for the separation of m-cresol-isopropylbenzene in order to optimize the extraction process conditions for the extraction of phenolic compounds in the 100−220 ℃ fraction section of direct coal liquefaction oils, and to investigate the recycling performance of DESs. Results showed that all the 3 DESs extractants had strong hydrogen bonding with m-cresol, while there was repulsion with isopropylbenzene; hydrogen bond was the driving force for the phenol extraction of ChCl∶EG(1.0∶1.5), and the hydrogen bond energy of ChCl∶EG(1.0∶1.5) with m-cresol was 7.76 kJ/mol, which was comparable to that of the calculation of COSMO-RS model, 7.62 kJ/mol. The extraction experiments of ChCl∶EG(1.0∶1.5) DESs showed that the product of partition coefficient and selectivity coefficient was up to 62165, and the viscosity was 46.59 mPa·s at 25 ℃, the extraction rate of m-cresol was 98.28%, and the entrapped isopropylbenzene was 4.99%, and after cycling for four times, the extraction rate of m-cresol was still 97.96%, which had a good performance in use; at the same time, the phenol extraction rate of 5 compounds complex model oils was 98.22%, and the entrapment of isopropylbenzene and tetrahydronaphthalene was 4.80%; the extraction rate of phenolic compounds in the 100−220 ℃ fractions of real direct coal liquefaction oils was 99.10%, and the entrapment rate of neutral oil was 8.38% for the ChCl∶EG(1.0∶1.5) DESs.