A novel approach toward the construction of multicomponent two-dimensional (2-D) and three-dimensional (3-D) metallosupramolecules is reported. Simply by mixing carboxylate and pyridyl ligands with cis-Pt(PEt3)(2)(OTf)(2) in a proper ratio, coordination-driven self-assembly occurs, allowing for the selective generation of discrete multicomponent structures via charge separation on the metal centers. Using this method, a variety of 2-D rectangles and 3-D prisms were prepared under mild conditions. Moreover, multicomponent self-assembly can also be achieved by supramolecule-to-supramolecule transformations. The products were characterized by P-31 and H-1 multinuclear NMR spectroscopy, electrospray ionization mass spectrometry, and pulsed-field-gradient spin echo NMR techniques together with computational simulations.