We previously reported the selective simultaneous separation of the substrates and products of a transesterification reaction (vinyl butyrate, 1-butanol, butyl butyrate and butyric acid) through supported liquid membranes (SLMs) based on 1-n-alkyl-3-methylimidazolium cations combined with tetrafluoroborate, hexafluorophosphate and bis{(trifluoromethyl)sulfonyl}imide anions. The best results were obtained by the use of tetrafluoroborate based ionic liquids, which led us to further investigate the use of these new supported liquid membranes for the selective separation of different substrates and products of transesterification reactions. With this aim, the permeability of sixteen different organic compounds (vinyl esters, aliphatic esters, alcohols and carboxylic acids) through SLMs containing tetrafluoroborate based ionic liquids ([bmim(+)][BF4-] and [omim(+)][BF4-]) were evaluated. It was found that permeability increased as the alkyl chain length decreased for the same organic functional group. In addition, significant permeability differences were found between the different organic functional groups. As regards the operational stability of these SLMs, they were seen to be very stable when tested over eight continuous cycles of 48 h each. (C) 2009 Published by Elsevier B.V.