Sulfonated polyimides with tertiary nitrogen in the polymer backbone were synthesized with 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-diaminobiphenyl 2,2'-disulfonic acid, 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and diaminoacrydine hemisulfate. They were crosslinked with a series of dibromo alkanes to improve the hydrolytic stability. The crosslinked sulfonated polyimide films were characterized for their thermal stability, ion-exchange capacity (IEC), water uptake, hydrolytic stability, and proton conductivity. All the sulfonated polyimides had good thermal stability and exhibited a three-step degradation pattern. With an increase in the alkyl chain length of the crosslinker, IEC decreased as 1.23 > 1.16 > 1.06 > 1.01, and the water uptake decreased as 7.29 > 6.70 > 6.55 > 5.63. The order of the proton conductivity of the crosslinked sulfonated polyimides at 90 degrees C was as follows: polyimide crosslinked with dibromo butane (0.070) > polyimide crosslinked with dibromo hexane (0.055) > polyimide crosslinked with dibromo decane (0.054). The crosslinked polyimides showed higher hydrolytic stability than the uncrosslinked polyimides. Between the crosslinked polyimides, the hydrolytic stability decreased with an increase in the alkyl chain length of the crosslinker. The crosslinked and uncrosslinked sulfonated polyimides exhibited almost the same proton conductivities. (c) 2005 Wiley Periodicals, Inc.