Pervaporation separation is one of promising membrane technology for the energy saving processes and it has been developed to separate complex mixture systems including azeotropic mixture, close-boiling mixture, aqueous organic mixtures etc. Many researchers focused on dehydration pervaporation separation and they commercialized ethanol dehydration and isopropanol recycling processes. Nowadays, petroleum separation and volatile organic compound removal using pervaporation membranes is one of the emerging application of pervaporation separation. We reviewed the development and application of pervaporation membranes.