Tributyl phyosphate(TBP) polypropylene glycol 4000(PPG-4000) and the mixture of two compounds were examined as a liquid membrane in a supported liquid membrane (SLM) to separate phenol from aqueous solution.The feed concentration of phenol was varied in a broad range from 500 mg/L to 5000 mg/L and different types of liquid membrane were prepared to elucidate their effects on separation of phenol. It was found that the modified PPG 4000 with TBP and toluene diisocyanate(TDI) might be used as a proper liquid membrane because the mass transfer rate examined with this membrane was higher than that through methyl isobutyl ketone (MIBK) which has been used as a conventional solvent in a solvent extraction process. The breakthrough pressure of the SLM is defined to be the pressure difference across the membrane at which the supported liquid membrane is not kept in the pores any more. it indicates how the SLM is stable., It was found that the breakthrough pressure of the modified PPG-4000 was much higher than those of typical organic solvents.