A sulfonated derivative of polybenzimidazole is reported, and its properties are analyzed in comparison with related polybenzimidazole proton-conducting materials. Poly(2,5-benzimidazole), poly(m-phenylenebenzobisimidazole), and poly[m-(5-sulfo)-phenylenebenzobisimidazole] were prepared by condensation of the corresponding monomers in polyphosphoric acid. Several adducts of these polymers with phosphoric acid were prepared. The resulting materials were characterized by chemical analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis; also, the dc conductivity of doped and undoped derivatives was measured. Similar to what has been observed for the commercial polybenzimidazole polymer (also examined here for comparison), the title polymers exhibit high thermal stability. Furthermore, their doping with phosphoric acid leads to a significant increase in conductivity from less than 10−11 Scm−1 for the undoped polymers to 10−4 Scm−1 (both at room temperature) for their acid-loaded derivatives. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3703–3710, 2002