The performance of poly(4-methyl-2-pentyne) (PMP)/silica nanocomposites was studied for membranes with a filler content between 10 and 40 wt%. An increase in permeability and a constant vapor selectivity were measured with increasing filler content. The constant selectivity was in contrast to earlier published results for silica filled poly(l-trimethylsilyl-l-propyne) (PTSMP) membranes. Therefore, a comparison between both materials was made. Free volume sizes and interstitial mesopore sizes were determined by use of positron annihilation lifetime spectroscopy (PALS) and image analysis was performed on transmission electron microscopy (TEM) pictures of both materials. Although both materials possessed interstitial mesopores, a difference in membrane structure was noticed, explaining the difference in membrane performance. (c) 2008 Elsevier B.V. All rights reserved.