Chitosan hollow fiber membranes (CHFMs) were successfully fabricated by a phase inversion method. The CHFMs obtained by ethanol-hexane exchange drying displayed integrally skinned asymmetric morphologies by field-emission scanning electron microscope observation. The CHFMs could be used for the pervaporation separation of dimethyl carbonate (DMC)/methanol mixtures. Swelling properties of the polymer material were investigated, and the effects of feed composition and operating temperature on the pervaporation separation performance of the CHFMs were evaluated. The relationship of permeation flux and temperature was in agreement with the Arrhenius equation. It was demonstrated that the integrally skinned asymmetric CHFMs exhibited an effective method for the separation of DMC/methanol azeotropic mixtures. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 2875-2882, 2010