A siloxane/polydimethylsiloxane (PDMS) hybrid membrane containing fluorinated side chains was prepared by a convenient and mild solgel process and a crosslinking reaction. The effects of the supercritical carbon dioxide (scCO2) conditions (i.e., treatment temperature, treatment time, and treatment pressure) on the permeation properties of fluorinated PDMS containing hybrid membrane were investigated. The chemical structure, microstructure, and physical performance of the membranes treated before and after were also discussed. The chemical structure of the PDMS membranes did not change with the scCO2 treatment conditions. The membranes still retained better membrane-forming abilities, higher permeability, and selectivity than normal PDMS membranes. Compared to those of the membrane with membrane formation after scCO2 treatment, the oxygen permeability coefficient and oxygen/nitrogen separation factor of the membrane with scCO2 treatment before membrane formation were higher and were up to 7.11 x 108 cm3 (STP) cm/(cm2 s cmHg) and 3.27, respectively. The permeation properties of the hybrid membrane were obviously higher than those of Robeson's upper bound. The high air-purification performance of the hybrid membrane may have been due to the introduction of fluorine atoms into PDMS membrane, and the increase in free volume resulted from the plasticizing function of the scCO2 treatment. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013