A novel aromatic trifluoromethylated diamine containing various functional groups was synthesized and characterized by using different spectroscopic techniques. The diamine was polymerized with various dianhydrides in a green media of ionic liquid (IL) without using NMP–pyridine–acetic anhydride. The poly(ether–imidazole–imide) (PEII)s were obtained in good yields (80–96%) with moderate viscosity (0.33–0.67 dL g1) in a shorter reaction time (10 h vs. 36 h) in IL. The resulting polymers were fully characterized and their properties such as solubility, viscosity, crystallinity, thermal, photophysical, and electrochemical behavior were investigated. They were amorphous and showed excellent solubility even in common organic solvents, such as chloroform and m-cresol, with ability to form tough and flexible films. The films were colorless and exhibited high optical transparency, with the UV cutoff wavelength in the range 304–337 nm and the wavelength of 80% transparency in the range 375–400 nm. Furthermore, they also possessed good thermal and thermo-oxidative stability with 10% weight loss temperatures (T10%) in the range 441–528 8C in N2 atmosphere and in the range 382–494 8C in air. The glass transition temperatures of all polyimides are in the range 204–302 8C. Their electrochemical behavior was also studied by using adsorptive stripping cyclic voltammetry and impedance spectroscopy on the multi-walled carbon nanotube-modified glassy carbon electrode.