Observation of adhesion layer between rubber and brass was done by using X-ray high resolution photoelectron spectroscopy. This study focuses on formation of sulfur derivatives in the adhesion layer during sulfuration reaction. Formation of CuxS (≃2) in the adhesion layer was observed at the very beginning of vulcanization. In addition, the amount of CuxS (≃2) was especially on the outermost surface of the adhesion layer, resulting from the reaction between copper and sulfur in rubber. Then CuxS (≃2) chemically changed to CuS in the deep part of the adhesion layer due to a presence of excess sulfur. Finally, ZnS was also formed in the deep part of the adhesion layer, as the vulcanization reaction excessively proceeded. The change of the chemical composition and distribution in the interface layer was observed by direct observation of S2p spectra using PES and XPS.