Polydimethylsiloxane pervaporation membrane was employed to remove ethanol from aqueous solutions. The influences of feed flow rate, temperature, permeate-side pressure, and ethanol concentration on the membrane performance were investigated. The feed flow rate was shown to have no significant effect on either flux or ethanol selectivity whereas the feed concentration, temperature, and permeate-side pressure had highly significant effects. Sorption and desorption experiments were also performed to provide data for analysis of mass transport based on resistance-in-series model. The analysis of transport resistances revealed that the mass transport of the system was controlled by the transport resistance of components in the membrane active layer.