Five different fluorinated polyimides were characterized using X-ray photoelectron spectroscopy (XPS). Elemental compositions and polyimide stoichiometries as elucidated with XPS are reported. The fluorinated polyimides derived from corresponding poly(amic acid)s were completely imidized after thermal cure at 350 degrees C, giving rise to a single N 1s peak at 400.8 eV. Interestingly, fluorine segregation on the cured polyimide surface was found to be a function of the polyimide backbone stiffness.