: Pervaporation (PV) is one of the most important membrane separation over last decade. It has developed as an effective tool for separation and recovery of liquid mixtures. Performance of this system is greatly influenced by the characteristic and behavior of the membrane. The most commonly used hydrophobic membrane for recovery of volatile organic compounds (VOCs) consists of a composite membrane with a selective layer of poly(dimethylsiloxane) (PDMS), also known as silicone rubber on a porous support layer. This membrane has high mechanical strength, thermal stability and suitable plasticity. The main challenge in applying PDMS rubbery membrane is its selectivity and permeability. Filling of the membrane is performed to modify the membrane and achieve high selectivity. In this study, the appropriate hydrophobic and organophilic fillers are used. Supramolecule calix[4]arene and one of its derivatives, calix[5]arene, silicalte-1, silica nanoparticles (10 and 80 nm), and hydrophobic silica are incorporated into the PDMS matrix supported by modified PES layer to improve the hydrophobicity of the membrane and enhance the separation factor. To obtain the optimum amount of adding fillers, the fabricated filled membranes are tested on a pervaporation setup. The results show that incorporating fillers will greatly enhance the enrichment factors of the filled membranes while a slight decrease in the permeation flux is observed. The highest enrichment factor for evey fillers was achieved as follows: 3748 by using 5% SiO 2 (10nm), 2608 by using 10% SiO 2 (80nm), 4744 by using 10% hydrophobic silica, 3250 by using 10% silicalite-1 and 4558 by using 5% calix[4]arene. The highest enrichment factor was achieved by adding 7.5 wt% calix[4]arene with butoxy in lower rim. The enrichment factor increases from 1123 to 5592 and normalized total flux decreases from 8906 to 5024 (gr/m 2 .hr) compared to the unfilled membrane. Finally, the effect of temperature and feed solution concentration on the pervaporation properties are also investigated by using the most selective membrane. The permeation fluxes of both toluene and water are increased with increase in the temperature and feed concentration. The increase in water flux with increasing feed concentration caused by swelling of the active layer with toluene. Moreover, because of the hydrophobicity of this filler, the enrichment factor is increased slightly. It was found that this behavior is completely different than PDMS without the filler. The plot of toluene, water and total fluxes against reciprocal of absolute temperature show good linearity and thus indicate agreement with the Arrhenius relationship. The overall activation energies of pervaporation are 0.9 and 40.18 kj/mol for toluene and water permeation fluxes, respectively