A promising new polydimethylsiloxane (PDMS)/organosilica hybrid membrane has been developed and applied to the removal of sulfur from model gasoline by pervaporation. The introduction of organosilicas derived from bis(triethoxysilyl)ethane (BTESE) into the PDMS matrix led to a simultaneous improvement of permeance and selectivity of the resultant membrane. The dual role of BTESE-derived organosilica networks as crosslinking agent and transport channel endowed the membrane with enhanced chain rigidity, appropriate free volume property and facilitated transport of permeating molecules. Swelling measurements confirmed that the PDMS/BTESE-derived organosilica hybrid membrane had a lower swelling degree than that of the PDMS control membrane. Moreover, effects of operational variables such as operating temperature, feed sulfur concentration, permeate pressure and feed flow rate on the desulfurization performances of the membranes were investigated. The PDMS/BTESE hybrid membrane exhibited superior durability in a continuous pervaporation operation of 80 h, showing the potential for the application in gasoline desulfurization. (C) 2016 Elsevier B.V. All rights reserved.