Depositing metal layers onto a self-assembled monolayer (SAM) is achieved using a new technique. Au(III) bearing a 4,4'-dithiodipyridine SAM is immersed into a Pd-II solution without potential control, causing Pd-II to adsorb on the surface by forming a complex with the pyridine species. The Pd-II ions are then electrochemically reduced to Pd-0 (see Figure). Angle-resolved X-ray photoelectron spectroscopy measurements unequivocally show that the reduced Pd resides on top of the SAM.