Phenols are common pollutants in many industrial wastewaters, posing tremendous harm to ecosystem. In this work, ternary extractant, containing tributyl phosphate/n-octanol/cyclohexane, was utilized to achieve the purpose of liquid-liquid extraction from phenol-bearing aqueous samples. Besides, respond surface methodology was employed to evaluate and further optimize the proportion of components. FT-IR spectroscopy results have demonstrated that the hydrogen bonding between tributyl phosphate and phenol make a great contribution to the extraction performance. At the optimized condition, the distribution coefficient could reach 622.1, whilst the residual Chemical Oxygen Demand of extractant is less than 77.4 mg/L. Eventually, an ultra-high extraction efficiency, up to 99.7%, was also proven for actual wastewater from coal tar processing.