Metallization methods of polyimide by hyperthermal atomic oxygen and atomic fluorine beams were developed.An atomic fluorine beam with a translational energy of 6.2 eV modified the wettability of polyimide surfaces to providean advancing water contact angle of 132°. It was confirmed that in-air storage for 2 months did not alter the hydrophobicproperty created by the atomic fluorine beam. This stable beam-induced surface fluorination technique was thenapplied to site-selective electroless Cu plating on polyimide. It was demonstrated that changing the exposure sequencecould create both positive- and negative-type plating processes.