Studying self-assembled monolayers (SAMs) of organic compounds on metal electrodes is a rather emerging field in electrochemistry. The most famous candidates for these systems are thiols on gold due to the strong Au−S interactions. Our institute concentrates on the metallization of such systems (but also non-thiol SAMs such as DCB, Fig. 1), which are investigated by cyclic voltammetry (CV) and scanning tunneling microscopy (STM). In different projects we investigate approaches to achieve the metallization of these systems. We were able to deposit a monolayer of metal on top of a variety of different SAMs. The resulting metal−molecule−metal sandwich structures show unique properties for tuning the electrochemical double layer or for catalytic reactions. We can even go further and form a molecular double decker by extending the SAM structure into the third dimension (Fig. 2). The formation of such nanoscale devices is not only of interest for fundamental electrochemistry but also for different industrial applications.