The performance of defect-free cross-linkable polyimide asymmetric hollow fiber membranes was characterized using an aggressive feed stream containing up to 1000ppm toluene. The membrane was shown to be stable against toluene-induced plasticization compared with analogs made from Matrimid®, a commercial polyimide. Permeation and sorption analysis suggest that the introduction of toluene vapors in the feed subjects the membrane to antiplasticization, as the permeance decreases significantly (to less than 30%) under the most aggressive conditions tested. Separation efficiencies reflected by permselectivities were less affected. The effect of the toluene on the membrane was shown to be reversible when the toluene was removed. © 2010 Elsevier B.V.