It is shown that ultra-thin multi-compound metal films (sandwich-structured Me films and surface alloys) can be formed by UPD and OPD in different multi-component systems using special polarization routines. The thickness, structure and composition of multi-compound metal films can be controlled by the choice of the substrate, the composition of the electrolyte, and the polarization conditions. The results obtained are of interest for the nanotechnology dealing with structuring and modification of metal surfaces in the nanometre range in the vertical and lateral directions.