We report the physical characteristics and gas transport properties for a series of pyrolyzed membranes derived from an intrinsically microporous polyimide containing spiro-centers (PIM-6FDA-OH) by step-wise heat treatment to 440, 530, 600, 630 and 800 degrees C, respectively. At 440 degrees C, the PIM-6FDA-OH was converted to a polybenzoxazole and exhibited a 3-fold increase in CO2 permeability (from 251 to 683 Barrer) with a 50% reduction in selectivity over CH4 (from 28 to 14). At 530 degrees C, a distinct intermediate amorphous carbon structure with superior gas separation properties was formed. A 56% increase in CO2-probed surface area accompanied a 16-fold increase in CO2 permeability (4110 Barrer) over the pristine polymer. The graphitic carbon membrane, obtained by heat treatment at 600 degrees C, exhibited excellent gas separation properties, including a remarkable CO2 permeability of 5040 Barrer with a high selectivity over CH4 of 38. Above 600 degrees C, the strong emergence of ultramicroporosity (<7 angstrom) as evidenced by WAXD and CO2 adsorption studies elicits a prominent molecular sieving effect, yielding gas separation performance well above the permeability-selectivity trade-off curves of polymeric membranes. (c) 2013 Elsevier Ltd. All rights reserved.