Polymer membranes containing alpha-cyclodextrin (alpha-CD) were prepared by the casting method using cross-linking reaction with hexamethylenediisocyanate. The film synthesis conducted with and without dibutyltin dilaurate as catalyst, resulted in two series of materials in which alpha-CD host entities were chemically linked to polyvinyl alcohol and physically entrapped, respectively. The obtained membranes were successfully applied to the separation of o-/p- and o-/m-xylene isomer mixtures by pertraction from water. p- and m-xylenes were found to be the faster permeants compared to the o-isomer. The separation factor of p-xylene over o-xylene varied from 7.75 to 0.35 depending on the membrane alpha-CD content and the feed concentration ratio. Permeation rate and separation selectivity data were discussed in terms of molecular recognition by alpha-CD and of coupling transport effect. Both kinds of materials showed similar behaviour in their permeation performances indicating that inclusion interaction was not changed by the chemical grafting on PVA chains. (c) 2005 Elsevier Ltd. All rights reserved.