In the present work, experiments have been carried out with a focus to reduce the volume requirement of solvent by mixing with imidazolium based ionic liquids (ILs) for the solvent extraction of phenol, p-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol from aqueous solutions. The effect of aqueous phase pH (2–12), agitation speed (100–450 rpm), solute concentration in feed (2–50 mg/L), temperature (303–333 K), treat ratio (1–11), and 1-butyl-3-methyl imidazolium tetrafluoroborate [Bmim]+[BF4]− volume in tributyl phosphate (TBP; 0–0.7% v/v) on extraction of phenols has been studied and optimized. Parameters like strip phase pH (3–13) and stripping agent concentration (0.001–0.009 N) have also been studied for stripping of phenols from solvent phase. It has been found that 0.5% v/v of ionic liquid [Bmim]+[BF4]− in solvent TBP extracts more than 97.5% of phenol and chlorophenols from aqueous solutions with a treat ratio (aqueous to solvent phase ratio) of 5. Transport mechanism for extraction and stripping of phenol and chlorophenols using ionic liquid [Bmim]+[BF4]− has been discussed. The results show that by appropriate selection of extraction and stripping conditions, it is possible to remove nearly all phenols with a treat ratio of 5.