Procedures for Torlon® 4000T membrane formation were developed to provide attractive and repeatable xylene separation properties. Torlon® 4000T membrane films cast by our method were investigated in terms of thermally induced imidization, molecular weight enhancement, and solvent removal. After development of the Torlon® 4000T casting procedure, pervaporation of a xylene mixture (i.e. 30% para-xylene, 30% meta-xylene, 30% ortho-xylene, and 10% ethylbenzene) was performed in both Torlon® 4000T and post casting annealed Torlon® 4000T films. The xylene pervaporation in annealed Torlon® 4000T film at 200°C gave a permeability of 0.25 Barrer and a selectivity of 3.1 (para/ortho) and 2.1 (para/meta) respectively. A so-called " permeability collapse" reflecting an accelerated reduction in the free volume is consistent with significant temperature-induced changes in the films observed after thermal annealing at 300°C. This conditioning effect is induced by a combination of heat treatment and the presence of the interacting aromatic penetrants. Optical methods were used to verify that the density of annealed samples exposed to xylene for 5 days eventually increased, suggesting that the membrane is originally swollen upon initial xylene exposure, and then relaxes to a more densified, and more discriminating state. © 2010 Elsevier Ltd.