Hydrophobic membranes were developed from an interpenetrating network (IPN) of hydroxy terminated polybutadiene (HTPB) based polyurethane urea (PUU) with polymethyl methacrylate (PMMA). Porosity was generated in the HTPB based polyurethane urea membrane by lithium chloride incorporation. Two sets of hydrophilic membranes were also developed: one from crosslinked polyvinyl alcohol (PVA) using maleic acid and citric acid as crosslinking agents and the other from a series of polyethylene glycols (PEGs) based polyether urethanes. The membranes were characterized by FTIR, XRD, mechanical properties measurements, SEM analyses, contact angle measurement of membrane surface and porosity measurement. Pervaporation parameters of the above membranes were studied in order to test their suitability in separation processes. The hydrophobic membranes were used for the separation of phenols, chlorophenols and chlorinated aliphatic hydrocarbons by pervaporation. It was observed that 3 ppm 2,4-dichlorophenol in water could be reduced to 0.3 ppm 2,4-dichlorophenol using a PUU-PMMA IPN membrane of ~28 cm2 area and 150 μm thickness in 3 h. This membrane has shown high selectivity towards p-chlorophenol and 2,4-dichlorophenol at very low concentrations in feed. Feed concentration of p-chlorophenol was varied from 1000 ppm to 7000 ppm and that of 2,4-dichlorophenol was varied from 3 ppm to 4000 ppm. 57 % 2,4-dichlorophenol in permeate was obtained from 3 ppm concentration in feed compared to 87% 2,4-dichlorophenol in permeate from 1000 ppm in feed. Pervaporation studies were carried out by varying the temperature of feed, membrane thickness and PMMA content in the membrane. In pervaporation experiment, for selective removal of chlorinated volatile organic compounds such as 1,1,2,2-tetrachloroethane, chloroform, carbon tetrachloride, trichloroethylene, concentrations of VOCs in feed were varied from 100 ppm (0.01%) to 1000 ppm (0.1%). All the IPN membranes showed excellent separation performances of the chlorinated VOCs from water.