Liquid membranes immobilized in novel porous hollow fiber-based membranes were used as a support for the pervaporation process to increase the VOC selectivity and membrane stability. Volatile fermentation byproducts such as acetone, butanol, and ethanol present in low concentrations in synthetic aqueous solutions were separated by novel liquid membranes. The liquid membrane with model solutions (containing acetone-butanol-ethanol (ABE)) as well as a filtered solution from a fermentation broth (from ABE fermentation) by the pervaporation process were evaluated. Very high selectivity for the solvents was obtained in the permeate especially at higher feed temperatures > 50°C;, high stability of liquid membrane was observed. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).