Worldwide environment has resulted in a limit on the sulfur content of gasoline. It is urgent to investigate the desulfurization of gasoline. The polydimethylsiloxane (PDMS)/polyetherimide (PEI) composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope (SEM). The membranes were used for sulfur removal from gasoline by pervaporation. The effects of feed temperature, sulfur content in the feed and PDMS layer thickness oil membrane performance were investigated, and an activation energy of permeation was obtained. Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor. The total flux varied little with the increase of sulfur content in the feed, but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline, and then the variation was little. The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor. The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.