Abstract Mass transfer phenomenon that occurs in the pervaporation process when applied to the microemulsion breakdown, was confirmed by the results of inverse gas chromatography. The stationary phase for this study was polydimethylsiloxane (PDMS), a hydrophobic polymer employed as a membrane in the pervaporation technique. The retention times of the different molecule probes (toluene, cyclohexane, and n-butanol) gave an insight into the extent of the interactions between each of these molecules and the stationary phase; these molecules were the components of the two microemulsions in study. The infinite dilution conditions allowed to determine the thermodynamic and the chromatographic parameters γ ∞ (the infinite dilution activity coefficient), the Flory-Huggins parameter interactions χ 12 ∞ , and V g 0 (the specific retention volume), respectively. The magnitudes of the latter parameters threw some light on the permselectivity of the membrane in the pervaporation operation.