A bis(dithiocarbamato)copper(II) complex (CuDTC2) was built on Au{111} surfaces (sheets and electrode beads) using different building blocks in a layer-by-layer (LbL) procedure. The process was followed by AFM and cyclic voltammetry. Initially 4-piperidinemethanethiol, which was synthesized here for the first time, was self-assembled on a gold surface and a highly organized array was obtained. The resulting monolayer was treated with CS2 and NH3 to transform the NH groups of piperidine into dithiocarbamate groups (DTC) with the formation of an amphiphilic ligand (DTCpipS) with thiolate and DTC terminal anionic groups. Two reductive desorption peaks were observed in the cyclic voltammogram of self-assembled DTCpipS, a more intense peak at -0.87 V (thiolate group) and a broader, less intense peak at -0.68 V, corresponding to the desorption of the DTC group bound to the gold surface after the ligand made a similar to 180 degrees flip on the surface. Copper(II) and the morpholyldithiocarbamate anion were associated with self-assembled DTCpipS in order to complete the formation of the CuDTC2 complex on the gold surface. In the voltammogram of the LbL self-assembled CuDTC2 complex the reductive desorption peak at -0.68 V disappeared and one single peak was observed at -0.85 V. This corresponds to the reorientation of all of the DTCpipS dianions in order to coordinate to copper(II) through the DTC groups, leaving the self-assembly only through the thiolate groups. The complete formation of the LbL self-assembled CuDTC2 complex was confirmed by XPS and ToF SIMS, with a detected fragment corresponding to the whole complex.