Polymeric membranes subjected to the permeation of n-hexane were characterized and the influence of pretreatment with ethanol on the properties of the membranes was studied to assess membrane performance and stability. The results suggest that the selectivity of the membrane depends not only on the pore size, but also to a great extent on the interaction between solvent and polymer. An increase in membrane roughness and contact angle was observed for all membranes after pretreatment with ethanol and n-hexane permeation. Moreover, the surface free energy decreased after solvents exposure, indicating an increase in membrane surface hydrophobicity and polymer swelling. The studied membranes show feasibility of use for the recovery of solvents, if suitable process parameters are selected.