The synthesis and characterization of new acid-base polymer blend membranes for the use in polymer electrolyte membrane fuel cell is presented in this paper. A novel polymeric base is synthesized from 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2-bis [4-(4-aminophenoxy)phenyl] hexafluoropropane and diaminoacrydine hemisulfate where the diaminoacrydine hemisulfate contribute the tertiary nitrogen groups to the polyimide backbone. This base polyimide is blended with a polyimide having sulfonic acid group in the main chain. The sulfonated polyimide is synthesized from 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTDA), 4,4'-diaminobiphenyl 2,2'-disulfonic acid (BDSA), 2-bis [4-(4aminophenoxy)phenyl] hexafluoropropane (HFBAPP). Various polyimide blends having different molar ratio of sulfonic acid group and acrydine group are synthesized and they are characterized for thermal stability, ion exchange capacity, water uptake, hydrolytic stability and proton conductivity. All the sulfonated polyimides have good thermal stability and exhibited three-step degradation pattern. With the increase in polymeric base content, IEC decreased as AB-0% (2.0640)> AB-10% (2.0058)> AB-20% (1.8792)> AB-30% (1.5686)> AB-40% (1.2670)> AB-50% (1.1690 > AB-75% (0.9098) and water uptake decreased as AB-0% (34.06%)> AB-10% (32.82%)> AB-20% (24.01%)> AB-30% (20.31%)> AB40% (12.86%)> AB-50% (9.25%)> AB-75% (8.37%). Proton conductivity of the acid-base polyimide blends at 90 degrees C are AB-0% (0.197)> AB10% (0.124)> AB-20% (0.122)> AB-30% (0.088)> AB-40% (0.080)> AB-50% (0.034)> AB-75% (0.025). Polyimide blends showed higher hydrolytic stability than the pure acid polyimide. Between the polyimide blends the hydrolytic stability increased with increase in the base polymer content which is attributed to the increase in ionic crosslink density which reduces the polymer swelling and hence the mechanical stability of the membrane increases. (c) 2006 Elsevier B.V. All rights reserved.