Using a process-guided approach, a new 6FDA-based polyimide - 6FDA-DAM:DABA(4:1) - has been developed in the form of hollow fiber membranes for CO 2 recovery from post-combustion flue gas streams. Dense film studies on this polymer reveal a CO 2 permeability of 224 Barrers at 40 °C at a CO 2 feed pressure of 10psia. The dense films exhibit an ideal CO 2/N 2 permselectivity of 20 at 40 °C, which permits their use in a two-step counter-flow/sweep membrane process. Dry-jet, wet-quench, non-solvent-induced phase inversion spinning was used to create defect-free hollow fibers from 6FDA-DAM:DABA(4:1). Membranes with defect-free skin layers, approximately 415nm thick, were obtained with a pure CO 2 permeance of 520GPU at 30 °C and an ideal CO 2/N 2 permselectivity of 24. Mixed gas permeation and wet gas permeation are presented for the fibers. The CO 2 permeance in the fibers was reduced by approximately a factor of 2 in feeds with 80% humidity. As a proof-of-concept path forward to increase CO 2 flux, we incorporated microporous ZIF-8 fillers into 6FDA-DAM:DABA(4:1) dense films. Our 6FDA-DAM:DABA(4:1)/ZIF-8 dense film composites (20wt% ZIF-8) had a CO 2 permeability of 550 Barrers and a CO 2/N 2 selectivity of 19 at 35 °C. Good adhesion between the ZIF and the 6FDA-DAM:DABA(4:1) matrix was observed. CO 2 capture costs of $\$$27/ton of CO 2 using the current, "non-optimized" membrane are estimated using a custom counterflow membrane model. Hollow fiber membrane modules were estimated to have order-of-magnitude reductions in system footprint relative to spiral-wound modules, thereby making them attractive in current space-constrained coal-fired power stations. © 2012 Elsevier B.V.