Vibrational spectroscopy has been applied to the benzenethiol molecule adsorbed on the silver surface. The results of infrared and Raman spectral studies have led to the conclusion that benzenethiol is chemisorbed dissociatively on the silver surface by rupture of S-H bond and the benzenethiolate formed upon adsorption is bound to silver via its sulfur atom. It seemed more likely that benzenethiol is adsorbed as being inclined to the silver surface. On contact with oxygen, the geometry of the adsorbed species appeared to bear a resemblance to that of silver benzenethiolate salt. The infrared bands of adsorbed species remained with little decrease of intensity even after the prolonged evacuation at 673 K, indicating that benzenethiol is very strongly chemisorbred to the silver surface.