A Cu (400 Å)/Al (50 Å)/polyimide system showed larger adhesion strength than that of Cu (400 Å)/polyimide after N2+ ion beam mixing. X-ray emission spectroscopy was performed to elucidate the mechanism of adhesion enhancement of the ion beam mixed Cu (400 Å)/polyimide with a thin Al buffer layer. Cu L2,3 x-ray emission spectra showed the formation of a CuAl2O4 layer which is strongly correlated with the large adhesion strength of a Cu/Al/polyimide. A decrease in adhesion strength at an ion dose higher than 5×1015 cm−2 was also explained by the formation of an amorphous carbon. This was understood by investigating C Kα x-ray emission spectra. The overall spectroscopic results were in accordance with the behavior of quantitative adhesion strength.