A cost-effective solvent extraction process for recovery of phenol and its hydroxy derivatives from aqueous medium was developed. Four different solvents—Tributyl phosphate (TBP), Triphenyl phosphate (TPP), Methyl isobutyl ketone (MIBK) and Oleic acid (OA)—selected based on their miscibility with water. The extraction efficiency (EE) of the selected solvents was studied. A reversed-phase HPLC system connected to an RP, C18 column was used to analyze the aqueous medium to evaluate the performance of the selected solvents. TBP exhibited the best extraction performance, while TPP and MIBK proved to be good when large amount of solvent was used. However, OA was found to be inefficient to extract the solutes under investigation. Interestingly, a different salvation property was observed and elucidated using the solvation theory.​