Technology designed to capture and store carbon dioxide (CO2) Will play a significant role in the near-term reduction of CO2 emissions and is considered necessary to slow global warming. Nanoporous carbon (NPC) membranes show promise as a new generation of gas separation membranes suitable for CO2 capture. We have made supported NPC membranes from polyfurfuryl alcohol (PFA) at various pyrolysis temperatures. Positron annihilation lifetime spectrometry (PALS) and wide angle X-ray diffraction (WAXD) results indicate that the pore size decreases whilst the porosity increases with increasing pyrolysis temperature. The membrane performance results support these findings with a significant increase in permeance being seen with increasing pyrolysis temperature, which relates to the increase in porosity. Mixed gas performance measurements also show an increase in CH4 permeance as the operating temperature is increased from 35 to 200 degrees C, which can be related to an increase in the rate of diffusion. However, the selectivity decreases with increasing operating temperature due to the smaller changes in the CO2 permeance. These smaller changes in CO2 permeance can be related to the stronger adsorption of this gas on the carbon surface at lower operating temperatures. Interestingly, regardless of the original pyrolysis temperature, the selectivity at higher operating temperatures is similar, whereas the permeance remains related to this pyrolysis temperature. (c) 2008 Cooperative Research Centre for Greenhouse Gas Technologies. Published by Elsevier B.V. All rights reserved.