Two new kinds of fluorine-containing poly-benzimidazoles (PBI), poly(2,2'-(tetrafluoro-p-phenylene)-5,5'-bibenzimidazole) and poly(2,2'-tetradecafluoroheptylene-5,5'-bibenzimidazole), were synthesized by condensation polymerization of 3,3'-diaminobenzidine and perfluoroterephthalic acid (or perfluoroazelaic acid), with polyphosphoric acid as solvent. Thermogravimetric analysis results show that the fluorine-containing polymers synthesized exhibit promising thermal stability. The film-forming properties of the fluorine-containing polymers are improved over nonfluorinated PBI. The introduction of fluorine into the backbone of the polymers has significant positive affection on their chemical oxidation stability demonstrated by Fenton test. Compared with poly(2,2'-(m-phenylene)-5,5'-bibenzimidazole)/phosphoric acid (PA) composite membrane, the resulting fluorinated membranes with a same PA doping level exhibit better flexibility and higher proton conductivity. The maximum proton conductivity gained is 3.05 x 10(-2) S/cm at 150 degrees C with a PA doping level of 7. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2115-2122, 2010