We report unique self-assembled monolayers (SAMs) consisting of dendritic viologen-arranged molecules with an omega-mercaptodecyl group (An, n (dendritic generation) = 0-3) at the apex of the dendritic structure, which can accommodate a specific amount of metal anionic complexes defined by the dendritic structure. Dendritic molecules from several generations were successfully synthesized via microwave heating, thus providing easy access to third-generation molecules without requiring protection/deprotection processes during generation growth. SAMs of the dendritic molecules were fabricated by soaking gold substrates in solutions of the molecules in an acetonitrile/ethanol mixture at room temperature. Counter anions of the viologen units in the SAMs could be exchanged easily for various metal anionic complexes, such as PtCl42-, CuCl42-, and PdCl42-, by immersing the SAMs in aqueous solutions of the ions. X-ray photoelectron spectroscopy of the SAMs revealed that the amount of the metal anionic complexes accommodated was dominated by the dendritic generation.