A novel fluorinated aromatic diamine, 1,1-bis(4-amino-3,5-dimethylphenyl)-1-(3,5-ditrifluoromethylphenyl)-2,2, 2-trifluoroethane (9FMA), was synthesized by the coupling reaction of 3', 5'-ditrifluoromethyl-2,2,2-trifluoroacetophenone with 2,6-dimethylaniline under the catalysis of 2,6-dimethylaniline hydrochloride. A series of fluorinated aromatic polyimides were synthesized from 9FMA and various aromatic dianhydrides, including pyromellitic dianhydride, 3,3'4,4'-biphenyl tetracarboxylic dianhydride, 4,4-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), and 4,4'-hexafluoroisopropylidene diphthalic anhydride, via a high-temperature, one-stage imidization process. The inherent viscosities of the polyimides ranged from 0.37 to 0.74 dL/g. All the polyimides were quickly soluble in many low-boiling-point organic solvents such as tetrahydrofuran, chloroform, and acetone as well as some polar organic solvents such as N-methyl-2-pyrrolidinone, N,N'-dimethylacetamide, and N,N'-dimethylformamide. Freestanding fluorinated polyimide films could be prepared and exhibited good thermal stability with glass-transition temperatures of 298-334 degrees C and outstanding mechanical properties with tensile strengths of 69-102 MPa and elongations at break of 3.3-9.9%. Moreover, the polyimide films possessed low dielectric constants of 2.70-3.09 and low moisture absorption (< 0.58%). The films also exhibited good optical transparency with a cutoff wavelength of 303-351 nm. One polyimide (9FMA/BTDA) also exhibited an intrinsic negative photosensitivity, and a fine pattern could be obtained with a resolution of 5 pm after exposure at the i-line (365-nm) wavelength. (c) 2006 Wiley Periodicals, Inc.