Composite membranes with a sub-nanoscale homogeneous distribution of CD toroids in the Matrimid matrix were developed for dehydration of aqueous isopropanol. The composite membranes demonstrated separation factor far surpassing that of the neat Matrimid dense membrane. The heart of this innovation is the utilization of a CD derivative, ethylenediamine-beta-cyclodextrin (EDA-beta-CD), where the amine of CD could react with the imide of Matrimid and efficiently immobilize the CD rings during membrane formation. The superior separation properties for membranes embedded with 2-5% EDA-beta-CD were attributed to the additional water channels created by the hydrophilic outer surface of CD and its interactions with the polymer matrix. FT-IR, density measurements and XRD have confirmed these hypotheses. Nevertheless, the separation factor exhibited an increasing then decreasing trend as a function of CD content and the opposite trend was observed with permeation flux. Investigation on the effect of feed water concentration showed that the neat Matrimid membrane possessed almost constant performance, but the Matrimid/EDA-beta-CD (0.05) composite membrane exhibited an obvious increase in permeability and a decrease in selectivity at high water content. Even though the composite membrane swelled more at higher water content due to the intensified hydrophilicity ascribed to the introduction of CD structure, it always had much better separation factor. In addition, the Matrimid mixed matrix membranes embedded with 2-5% EDA-beta-CD held reasonably tensile strength and modulus. The newly developed mixed matrix membrane approach may open up a new way to prepare next-generation high-performance asymmetric pervaporation membranes for isopropanol separation. (C) 2009 Elsevier B.V. All rights reserved.