A hollow fiber supported liquid membrane (HFSLM) method was developed to extract organic pollutants (ethylbenzene and nitrobenzene) from aqueous solution, which provided a high selectivity and extraction efficiency. It was a two-phase system. The microporous hydrophobic polyethersulfone (PES) hollow fiber membrane which was made in our laboratory was used as the solid support for the liquid membrane. n-undecane, n-dodecane, n-heptanol and n-octanol were used as organic extractants which were located inside the pores and the lumens of the hollow fibers. The organic pollutants were extracted from aqueous phase into organic phase. A new approach of choosing the organic extractants which was based on Hansen Solubility Parameters (HSP) theory was proposed. The selectivity and extraction performance of organic extractants to ethylbenzene and nitrobenzene were successfully related to HSP values. The effect of different parameters such as operation temperature, flow rates of aqueous phase and organic phase, initial concentration of organic pollutants and pH value in aqueous phase was also studied. (c) 2008 Elsevier B.V. All rights reserved.