A novel technique has recently been presented for depositing metal layers onto a SAM. This is demonstrated here for Pd and Pt deposits on a mercaptopyridine (4-PyS) SAM. The SAMcovered Au(111) electrode is immersed into the metal-ion-containing solution without potential control. As a result, metal ions, e.g., Pd(II) (respectively Pt(II)) adsorb on the surface by forming a complex with the pyridine species. Subsequently, the electrode is transferred to a metal-ion-free solution, where the adsorbed metal ions are reduced electrochemically to its zero-valent state. Upon reduction, monoatomic high metal islands were observed in STM. Angle resolved XPS measurements show unequivocally that the reduced metal resides on top of the SAM.