The bottom-up fabrication of molecular devices with vertical or lateral structure is one of the most challenging research subjects. For the fabrication of vertical nanostructure, the layer-by-layer growth of redox-active complexes based on surface coordination chemistry is applied. In order to control the molecular orientation on the surface, a novel ligand with tetrapod phosphonate groups (XP) has been introduced. The combination of self-assembly and successive metal coordination leads to provide novel well-defined multilayer structures, which act as molecular rectifying devices or switches on surfaces. Layer-by-layer fabrication of mono- and dinuclear metal complexes with XP ligand on surface made it possible to control the multilayer structure on the surface. The combinatorial approach to multilayer structures by use of the redox-active molecular units can produce the various types of potential gradients on the surface, which lead to the rectifying or memory devices. For the construction of two-terminal lateral device structure, the interconnection of molecular dots on the terminal surface by DNA has been studied. The point-to-point capture of DNA by surface metal complex on mica or Au patterned SiO₂/Si wafer surface was successfully achieved, and the interconnected DNA acts as a scaffold for two-terminal lateral nanowiring.