An intrinsically microporous hydroxyl-functionalized polyimide (PIM-PI) made from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,6(7)-dihydroxy-3,7(6)-diaminotriptycene (DAT1-OH), was thermally converted to polybenzoxazole (PBO). The thermal rearrangement of the PIM-PI to PBO significantly increased the free volume, which was reflected by a boost in its microporosity as indicated by enhanced Brunauer-Emmett-Teller (BET) surface area from 167 to 405 m2 g−1. The increase in free volume noticeably improved the gas permeability but also resulted in reduced gas-pair selectivity. The fresh PBO membrane made by thermal treatment at 460 °C for 30 min (TRIP-TR-460-30) with a PBO conversion of 98% displayed a 20-fold higher CO2 permeability of 840 barrer than the initial value of 43 barrer for the 6FDA-DAT1-OH polyimide at the expense of ~ 60% decrease in pure-gas CO2/CH4 selectivity from 52 to 21. The TRIP-TR-460-30 PBO showed good performance for propylene/propane separation with pure-gas C3H6 permeability of 21 barrer and C3H6/C3H8 selectivity of 16 for a 28-days aged sample. When tested under mixed-gas conditions C3H6 permeability dropped to 12.8 barrer and C3H6/C3H8 selectivity of 8. TRIP-TR-460-30 PBO displayed mechanical properties comparable some rigid polyimides with tensile strength, Young's modulus and elongation at break of 58 MPa, 1.83 GPa and 4.3%, respectively.