Copper thin films were selectively fabricated on a Teflon surface by using an ArF excimer laser and a Cu electroless plating solution in open air. Photo-excited C-F bonds of the surface were effectively defluorinated with hydrogen atoms which were photodissociated from the Cu solution. The dangling bonds of the defluorinated carbon atoms were combined with the oxgen and the copper atoms which were also photodissociated. Thus, C-O-Cu bonds were formed on the surface and functioned as Cu nuclei for an electroless plating. The Cu thin films were successfully deposited in electroless plating solution only on the Cu nuclei.