The adsorption of methanethiol on a Ag(100) surface has been studied with Extended Huckel calculation in the cluster approximation of the substrate. Since it has been known that methanethiol is chemisorbed dissociatively on silver surface by rupture of S-H bond, the methanethiolate radical is taken as adsorbate. Of the various adsorption sites, the 4-fold hollow site is preferred. The methanethiolate radical is mainly adsorbed via its 2e orbital. The charge transfer from metal to this level leads to the C-S bond weakening, which is consistent with the red shift of C-S stretching mode in surface enhanced Raman (SER) spectrum.