In this article, dicationic ionic liquids (DILs), including N,N,N,N',N',N'-hexaethyl-ethane-1,2-diammonium di-bromide (HEDBr), N,N,N,N',N',N'-hexaethyl-propane-1,3-diammonium dibromide (HPDBr) and N,N,N,N',N',N'-hexaethyl-butane-1,4-diammonium dibromide (HBDBr), were designed and used to extract phenolic compounds from model oil and coal tar oil. The effects of stirring time, temperature, DIL:phenol mole ratio, and initial phenol concentration on the extraction of phenol were studied. It is found that the DIL:phenol mole ratio is only around 0.3 when the highest extraction efficiency of phenol is obtained. The extraction process completes within 5 min at room temperature, and the extraction efficiency is not dependent on temperature. Also, the ultimate phenol concentration remains constant despite the difference in initial phenol concentrations. Of these DILs, HPDBr shows the lowest ultimate phenol concentration of 3.9 g/dm(3), and the extraction efficiency of phenol can reach as high as 97.0%. These DILs can be regenerated by anti-solvent method and reused several times without significant reduction in extraction efficiency. In addition, HPDBr was demonstrated to extract phenolic compounds from real coal tar oil, and its extraction efficiency of phenolic compounds is 92.7%. The mechanism, analyzed by FT-IR, shows that there is a hydrogen bond between phenol and DIL.