This work focused on the extraction of BTEX from aqueous solution by a hollow-fiber microporous membrane liquid/liquid extraction (HF-MMLLE) technique. A simple and rapid method based on the Hansen solubility parameters (HSP) theory was adopted to theoretically determine the interaction parameter (X-12) between the extractants and BTEX. Experiments were carried out to establish the relationship between the interaction parameter and the extraction performance. Furthermore, the distribution coefficient and permeability coefficient related to the extraction performance were also discussed, which verified the relationship from a quantitative idea. It: was observed that the liquid/liquid extraction was based on the strong affinities between the extractants and the target pollutants. This method should be paid more attention for its potential application in other solvent-sensitive processes.