A hydroxyl-functionalized triptycene-based polyimide of intrinsic microporosity (TDA1-APAF) was converted to a polybenzoxazole (PBO) by heat treatment at 460 °C under nitrogen atmosphere. TDA1-APAF treated for 15 min (TR 460) resulted in a PBO conversion of 95% based on a theoretical weight loss of 11.7 wt% of the polyimide precursor. The BET surface area of the TR 460 (680 m2 g−1) was significantly higher than that of the TDA1-APAF polyimide (260 m2 g−1) as determined by nitrogen adsorption at −196 °C. Heating TDA1-APAF for 30 min (TRC 460) resulted in a weight loss of 13.5 wt%, indicating full conversion to PBO and partial main-chain degradation. The TR 460 membrane displayed excellent O2 permeability of 311 Barrer coupled with an O2/N2 selectivity of 5.4 and CO2 permeability of 1328 Barrer with a CO2/CH4 selectivity of 27. Interestingly, physical aging over 150 days resulted in enhanced O2/N2 selectivity of 6.3 with an O2 permeability of 185 Barrer. The novel triptycene-based TR 460 PBO outperformed all previously reported APAF-polyimide-based PBOs with gas permeation performance close to recently reported polymers located on the 2015 O2/N2 upper bound. Based on this study, thermally-rearranged membranes from hydroxyl-functionalized triptycene-based polyimides are promising candidate membrane materials for air separation, specifically in applications where space and weight of membrane systems are of utmost importance such as nitrogen production for inert atmospheres in fuel lines and tanks on aircrafts and off-shore oil- or natural gas platforms. Mixed-gas permeation experiments also demonstrated good performance of the TR 460 membrane for natural gas sweetening with a CO2 permeability of ∼1000 Barrer and CO2/CH4 selectivity of 22 at a typical CO2 wellhead partial pressure of 10 bar.