A robust polyimide film was facilely fabricated on the ITO-glass substrate from the electrolyte solution of a bis (tiiphenylamine) perylene diimide by electrochemical polymerization. The cyclic voltammogram of the electrodeposited polyimide film shows ambipolar redox processes, with a reversible redox couple with a half wave potential (E-1/2) of + 0.99 V during the anodic scanning and two pairs of redox waves at E-1/2 = -0.41 V and -0.65 V during cathodic scanning. The electroactive film did not delaminate from the electrode upon cycling electrochemically between its oxidized/reduced and neutral states. The polyimide film exhibits stable anodic and cathodic coloring, with high optical contrast, high coloration efficiency, and good cycling stability.