The polyimide film surface was modified with KOH aqueous solutions or sulfuric acid. The film thickness was increased by about 10% through the modification of film surface. Hydrolysis of amide bonds and hydration of water induced the increase. The polarity of the film surface increased and identified by contact angle measurement. The depth and roughness of modified was increased. After treatment of surface with water, alkyl and 4-pentyloxyaniline were introduced on the film surface by complex formation between anionic species formed on the imide surface and ammonium ion. The newly introduced alkyl group was identified by FT-IR spectroscopy. Surface polarity reduced dramatically and the roughness was increased after introduction of ammonium salt.