The self-assembly of covalently linked dyad la of cyclometalated organoplatinum(II) complex and fullerene afforded alternating multilayers of electron-rich and -deficient molecular components. On the other hand, the coassembly of la with organoplatinum(II) complex 2 having no fullerene moiety gave an exfoliated form of the multilayers, by inhibiting the interdigitation of organoplatinum(II) complex moieties of la. The coassembled la/2 transports both of the photogenerated holes and electrons, while the self-assembled la allows only the transportation of electrons under the same conditions.