The transport properties of a unique family of silane-modified poly(vinyl chloride) (PVC) pervaporation membranes for the separation of halogenated hydrocarbons from water were investigated. The PVC was modified by using a vinyl silane to improve its resistance to attack by halogenated hydrocarbons and to increase the flux. Two preparation routes were used: Route i included an initiator to promote the vinyl reaction before the hydrolysis and condensation of the methoxy silane group, whereas Route ni did not. The structures of the membranes were characterized and related to the transport properties, as derived from batch pervaporation experiments. The permeability of unmodified PVC membranes increases with exposure to haloorganics at low concentrations. Initially, the modified membranes exhibited a higher permeability than PVC and a lower selectivity. At long pervaporation times, the silane-modified membranes exhibited a higher selectivity than PVC. The different preparation routes led to different morphologies, which affected the performance of the membranes; Route ni membranes exhibited higher permeabilities and selectivity than Route i membranes. Rubbery polydimethylsiloxane membranes were resistant to haloorganics but their high water permeability and low selectivity make them unsuitable for this pervaporative separation.