A series of sulfonated polyimide (SPI) copolymers containing methyl, methoxy, or fluorine groups were synthesized to elucidate the substituents effect on their proton conducting properties as well as thermal, hydrolytic, and oxidative stability for polymer electrolyte membrane fuel cell applications. SPIs of high molecular weight (M-w > 200 kDa, M-n > 80 kDa) along with the ion exchange capacity (IEC) varying between 1.34 and 1.91 mequiv/g were obtained, which gave tough, ductile, and flexible membranes by solution, casting. The thermal properties of the SPIs were dominated by the electronic structure of the sulfonated aromatic rings. The electron-donating methyl groups lowered the thermal decomposition temperature. The hydrolytic and oxidative stability was roughly in the order of IEC (the higher IEC membranes were less stable). Fluorine groups, either as -F or -CF3, had negative effect on the hydrolytic and oxidative stability. In the water uptake and proton conductivity, hydrophobic components are rather more influential than the substituents. It was found out that the SPI(5, 8, 0.7) containing bis(phenoxy)biphenylene sulfone moieties as a rigid hydrophobic component showed the best balanced properties in terms of the stability and the proton conductivity for its rather low IEC. (c) 2008 Wiley Periodicals, Inc.