Removal of benzene from pyrolysis gasoline is important to meet automobile emission specifications. EPA (Environmental Protection Agency) - MSAT (Mobile Source Air Toxic) requires refiners to meet an annual average benzene content of 0.62% by volume in gasoline. According to BS VI the maximum allowable concentration of benzene in pyrolysis gasoline should be less than 1% volume (max). A polyimide-polyaniline nanocomposite membrane was fabricated by solution casting a mixture of polyamic acid, N,N-dimethylacetamide and polyaniline. The prepared membrane was characterized by Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and swelling study. This membrane was utilized for the separation of benzene from model pyrolysis gasoline via pervaporation. About 80% benzene removal was achieved. Hence it can be concluded that the novel nanocomposite membrane fabricated using a simple and relatively inexpensive method has good potentiality for pervaporative removal of benzene from the chosen system.