Polybenzimidazoles (PBIs) are attractive membrane materials for H-2/CO2 separation at hydrocarbon fuel derived synthesis gas operating conditions due to their exceptional physicochemical stability and promising permselectivity character. PBI molecular structure modification is a viable approach to disrupt chain packing altering the free-volume architecture which results in improved gas transport characteristics. This work is focused on the synthesis and characterization of novel PBI random copolymers for application as elevated temperature H-2/CO2 membranes. The co-polymerization route is expected to result in tailorable permeability and selectivity by combining the high H-2 permeability aspect of the highly disrupted loosely packed hexafluoroisopropylidene diphenyl group containing PBI segments (6F-PBI) with the highly selective tightly packed phenylene group containing PBI segments (m-PBI). 6F/m-PBI copolymers with varying 6F-PBI and m-PBI ratios having high inherent viscosity were synthesized. The structure and ratio of the 6F- and m-PBI fractions were confirmed using FTIR and NMR spectroscopic techniques. The measured gas transport properties of copolymer thin films cast in controlled environment were measured as a function of the operating conditions. The H-2 permeability increased while H-2/CO2 selectivity decreased as the 6F-PBI copolymer fraction was increased. (C) 2017 Elsevier Ltd. All rights reserved.