A new diamine, 2,2′-bis(3,4,5-trifluorophenyl)-4,4′-diaminodiphenyl ether (FPAPE) was synthesized through the Suzuki coupling reaction of 2,2′-diiodo-4,4′-dinitrodiphenyl ether with 3,4,5-trifluorophenylboronic acid to produce 2,2′-bis(3,4,5-trifluorophenyl)-4,4′-dinitrodiphenyl ether (FPNPE), followed by palladium-catalyzed hydrazine reduction of FPNPE. FPAPE was then utilized to prepare a novel class of highly fluorinated all-aromatic poly(ether-imide)s. The chemical structure of the resulting polymers is well confirmed by infrared and nuclear magnetic resonance spectroscopic methods. Limiting viscosity numbers of the polymer solutions at 25 ◦C were measured through the extrapolation of the concentrations used to zero.Mn and Mw of these polymers were about 10 000 and 25 000 g mol−1, respectively. The polymers showed a good film-forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. An excellent solubility in polar organic solvents was observed. X-ray diffraction measurements showed that the fluoro-containing polymers have a nearly amorphous nature. The resulting polymers had Tg values higher than 340 ◦C and were thermally stable, with 10% weight loss temperatures being recorded above 550 ◦C. Based on the results obtained, FPAPE can be considered as a promising design to prepare the related high performance polymeric materials.