Polyhedral oligomeric silsesquioxanes (POSSs) are a promising family of regularly structured silsesquioxanes with resilient cage-like configurations and exterior edges that can be functionalized with various organic groups. In this study, POSS was functionalized with a polyimide−phenylene (PI−Ph) unit, which yielded POSS−PI−Ph to fabricate carbonized-POSS membranes (denoted as carbon-POSS) via inert pyrolysis. Replacing some PI−Ph units with norbornene (NB) increased the amount of residual carbon formed in the carbon-POSS structure. X-ray photoelectron spectroscopy and 29 Si nuclear magnetic resonance analysis revealed that residual sp 2 -hybridized carbon atoms were connected to the POSS cage after pyrolysis at 700 °C. Analysis of single-gas permeation at 200 °C with the carbon-POSS membranes pyrolyzed at different temperatures (200−800 °C) indicated that the permeance of all investigated gases (He, H 2 , CO 2 , N 2 , CH 4 , CF 4 , and SF 6 ) increased with increasing membrane pyrolysis temperature. Notably, the early onset of the decline in permeance of large-molecule gases such as CF 4 and SF 6 at 600 °C ensured a high N 2 permeance and ideal N 2 /SF 6 selectivity of 10 −6 mol m −2 s −1 Pa −1 and 100, respectively. Overall, this study demonstrates the feasibility of preparing high-performance carbon-POSS-derived membranes by optimizing the NB functionality and the POSS content of the hybrid copolymer precursor.