Three novel polyimides have been successfully synthesized horn 3,8-diphenylpyrene-1,2,6,7-tetracarboxylic dianhydride (DPPD), and three commercial diamines by solution polycondensation. All polymers exhibited high molecular weight, high thermal stability and high rigidity (no glass transition was detected up to 400 degrees C) and free volume. The new polymers have been tested as gas separation membranes, showing very good combination of permeability and selectivity, especially in the case of the polymer derived from trimethyl-m-phenylenediamine (TMPD), which overpassed the 1991 Robeson upper bound for the gas pairs O-2/N-2 and CO2/CH4 and was near the 2008 upper bound for CO2/N-2. (C) 2014 Elsevier B.V. All rights reserved.