A series of soluble, benzimidazole-based polymers containing sulfonic acid groups (SuPBI) has been synthesized. SuPBI membranes resist extensive swelling in water but are poor proton conductors. When blended with high ion exchange capacity (IEC) sulfonated poly(ether ether ketone) (SPEEK), a polymer that has high proton conductivity but poor mechanical integrity, ionic crosslinks form reducing the extent of swelling. The effect of sulfonation of PBI on crosslinking in these blends was gauged through comparison with nonsulfonated analogs. Sulfonic acid groups present in SuPBI compensate for acid groups involved in crosslinking, thereby increasing IEC and proton conductivity of the membrane. When water uptake and proton conductivity were compared to the IEC of blends containing either sulfonated or nonsulfonated PBI, no noticeable distinction between PBI types could be made. Comparisons were also made between these blends and pure SPEEK membranes of similar IEC. Blend membranes exhibit slightly lower maximum proton conductivity than pure SPEEK membranes (60 vs. 75 mS cm(-1)) but had significantly enhanced dimensional stability upon immersion in water, especially at elevated temperature (80 degrees C). Elevated temperature measurements in humid environments show increased proton conductivity of the SuPBI membranes when compared with SPEEK-only membranes of similar IEC (c.f. 55 for the blend vs. 42 mS cm(-1) for SPEEK at 80 degrees C, 90% relative humidity). (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3640-3650, 2010