Electrochemical deposition of metals ( platinum or gold) only on top of an organothiolate, 1,4-benzene-dimethanethiol (BDMT) or hexanedithiol (HDT), self-assembled monolayer (SAM) on a Au(111) substrate was achieved by electrochemical reduction of PtCl42- or AuCl4- ion, which was preadsorbed on one free thiol end group of the dithiol SAM formed on a Au surface, in a metal-ion-free sulfuric acid solution at potentials more negative than the reduction potential of the metal ion. Angle-resolved X-ray photoelectron spectroscopy (AR-XPS) measurement after the reduction of preadsorbed PtCl42- ion on BDMT/Au(111) electrode showed the presence of Pt not underneath but on top of the BDMT SAM. After a negative potential scan of the Pt/BDMT/Au(111) electrode to -1.30 V in 0.1 M KOH solution, a typical cyclic voltammogram of a clean Au(111) electrode was obtained, showing that the BDMT SAM with a Pt layer was reductively desorbed. These results proved that a Pt-BDMT SAM-Au substrate sandwich structure without a short circuit between the two metals was successfully constructed by this technique. Furthermore, a decanethiol (DT) monolayer was constructed on a Au layer, which was formed by the reduction of preadsorbed AuCl4 ion on HDT/Au(111) electrode. The formation of DT/Au/HDT/Au( 111) structure was confirmed as two cathodic peaks corresponding to reductive desorption of DT from Au on top of the HDT/Au( 111) at -0.97 V and that of Au/HDT from Au(111) at -1.12 V were observed when potential was scanned negatively to -1.35 V.