Two series of new redox-active aromatic polyimides with methyl- (–CH3) or trifluoromethyl (–CF3)-protecting triphenylamine moieties were prepared from 4,4′-diamino-4″-methyltriphenylamine and 4,4′-diamino-4″-(trifluoromethyl)triphenylamine with aromatic tetracarboxylic dianhydrides via the conventional two-step polycondensation technique. Flexible and strong polyimide films could be obtained via the thermal curing of their precursor poly(amic acid) films or direct solution cast from some organosoluble polyimides. The polyimides showed high glass-transition temperatures between 269°C and 312°C, and they did not show significant decomposition before 500°C in air or under nitrogen atmosphere. Cyclic voltammograms of the polyimide films on the indium–tin oxide-coated glass substrate exhibited a pair of reversible redox waves with half-wave oxidation potentials of 1.08–1.10 V (for the –CH3 series) and 1.23–1.26 V (vs. silver/silver chloride; for the –CF3 series) in acetonitrile solution. The polyimide films showed anodic electrochromism from pale yellow neutral state to purplish blue (for the –CH3 series) and chrome yellow (for the –CF3 series) when oxidized.