A thiolate self-assembled monolayer (SAM) was formed oil a metallized dithiol SAM, resulting in a new kind of metal-organic molecule bilayer. 1,6-Hexanedithiol (HDT) was adsorbed on a Au(111) surface followed by adsorption and electrochemical reduction of AuCl4- Oil the HDT SAM, and then by adsorption of 1-decanethiol. The formation of the bilayer was confirmed by Fourier transform infrared spectroscopy, sum frequency generation, and electrochemical measurements.