The removal of trace chlorinated and aromatic hydrocarbons from water by a pervaporation technique has been carried out through poly (dimethylsiloxane) membrane which had been fabricated by the addition crosslinking reaction. This study dealt with the swelling and permeation behaviors of the PDMS membranes with dichloroethane trichloroethane and toluene aqueous solutions. The swelling ratio in the toluene aqueous solution was much higher than those in the chloroethane solutions at all of the operating temperatures and concentrations. The solubility parameter theory was introduced to interpret the affinity between permeates and a membrane material and in all cases this approach seemed to be proper. It was suggested that the existence of water clusters in the membrane due to the hydrophobic characteristics of the membrane made the size of the permeating water larger resulting in suppressing water permeation and increasing enrichment of the organic components. The permeation behaviors at different membrane thicknesses were indirectly interpreted in terms of the effect of concentration polarization.