The application of octatrimethylsiloxy polyhedral oligomeric silsesquioxane (POSS) nanoparticles was investigated in the fabrication of novel reverse-selective poly(4-methyl-2-pentyne) (PMP) nanocomposite membranes for the separation of heavier hydrocarbons from methane. Generally, PMP and PMP–fumed silica (FS) nanocomposite membranes suffer severe physical aging with approximately 40% permeation flux reduction over 120 days. A straightforward strategy was introduced to suppress the physical aging of PMP and also to improve the thermal stability without compromising the selectivities and permeabilities through the incorporation of a functionalized POSS–FS binary filler system. Fourier transform infrared spectroscopy and scanning electron microscopy proved productive interactions between the fillers and polymer, with a fair compatibility between them. Thermogravimetric analysis confirmed that the thermal stability of the neat PMP was enhanced by the incorporation of the fillers into the nanocomposites. The addition of POSS and FS led to improved operational performance, such as in the permeability and selectivity, over the neat PMP. The permeation stabilities of the PMP–POSS and PMP–FS–POSS nanocomposite membranes were clearly improved over a long time (120 days). The permeation data indicated that the PMP–3 wt % POSS–20 wt % FS nanocomposite membrane is promising for
C3H8/N2 and C3H8/CH4 separation.