A novel extraction procedure has been developed for treating phenolic wastewater. Alcohols, amines, and organic acids were applied as extractants in separation of phenol from the wastewater containing 6000 mg/l phenol and 5% salts discharged by chemical plants, >99% phenol was recovered by extracting with octanol. The interactions of phenol with alcohols, amines, and organic acids were studied by a theoretical calculation with GAUSSIAN 98. The extraction efficiency is strongly dependent on the intermolecular interactions between the phenol and extractants. Based on the experimental and theoretical studies, a pilot-scale LLES was set-up and worked well. (C) 2003 Elsevier B.V. All rights reserved.