Polystyrene-co-divinylbenzene (PS-co-DVB) asymmetric membranes were prepared. In order to control their structure and mechanical properties the degree of cross-linking and the composition of casting solution were varied. The rubber added PS-DVB membranes was also prepared to overcome the mechanical limitation of cross-linked membrane, and their mechanical properties were investigated. It was revealed that the concentration of polymer in the casting solution affected the determination of skin formation. When the PS-co-DVB membrane consists of styrene-butadiene (SB) rubber or liquid polybutadiene (PBD), the structures formed showed that the PS content in the PS/DVB system played an important role in determining the porous sublayer structure.