Two novel aromatic tetraamines containing bulky lateral phenyl unit and multiple trifluoromethyl groups, 1,1-bis[4-(3′,4′-diaminophenoxy)phenyl]-1-(3″-trifluoromethylphenyl)−2,2,2-trifluoroethane (6FTA) and 1,1-bis[4-(3′,4′-diaminophenoxy)phenyl]-1-[3″,5″-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane (9FTA) were synthesized and characterized. A series of fluorinated aromatic polybenzimidazopyrrolones (polypyrrolones, PPys) were synthesized via a two-step polycondensation procedure. The inherent viscosities of the precursors, poly(amide amino acid) (PAAA), ranged from 0.39 dL/g to 0.54 dL/g. All the FPPys were amorphous. The freestanding FPPy films could be prepared, which exhibited good thermal stability with the glass transition temperature of 315–389°C, the temperatures of 5% weight loss (T5%) of 497–535°C in nitrogen and residual weight retention at 700°C over 60%. All the FPPy films exhibited excellent alkaline-hydrolysis resistance which retained their original shapes and toughness after boiling 7 days in 10% sodium hydroxide solution. Also after boiling 8 h in 10% sodium hydroxide solution, the tensile strength could retain as high as 56% of the original values. The alkaline-hydrolysis resistance was much better than the polyimides which had similar chemical structures. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40041.