Two novel bisphenols, 1,1-bis(4′-hydroxy-3′,5′-dimethylphenyl)-1-(3′′-trifluoromethylphenyl)-2,2,2-trifluoroethane (4M6FDO) and 1,1-bis(4′-hydroxy-3′,5′-dimethylphenyl)-1-[3′′,5′′-bis(trifluoromethyl)phenyl]-2,2,2-trifluoroethane (4M9FDO), with methyl groups ortho-substituted to the phenol groups, bulky trifluoromethyl-substituted phenyl groups and trifluoromethyl groups in the structure, were synthesized and characterized. The bisphenols were polymerized with 4,4′-difluorobenzophenone and bis(4-fluorophenyl) sulfone, respectively, via a aromatic nucleophilic substitution polycondensation to afford four poly(aryl ether ketone/sulfone)s (PAEKs/PAESs) with the inherent viscosities of 0.32–0.52 dL g⁻¹. The ortho-methyl and pendant trifluoromethyl-substituted phenyl groups endow the polymers with good solubility, the rigidity of the polymer chains increase the glass transition ( Tg) of the polymers to 197–235 °C. Flexible and tough films cast from N,N-dimethylacetamide showed good thermal stability, low dielectric constants of 2.67–2.73 and low water uptakes of 0.21–0.40%. Moreover, the polymers showed good transparency with light transmittance at 450 nm as high as 96% and cutoff wavelength as low as 285 nm. The PAEKs also exhibited low light-absorption at the optocommunication wavelengths of 1310 and 1550 nm.