A new class of 120 degrees dendritic di-Pt(II) acceptor subunits has been designed and synthesized, from which six-component hexagonal metallodendrimers were easily formed with 120 degrees dendritic dipyridine donors via [3 + 3] coordination-driven self-assembly. The structures of all metallodendrimers are confirmed by multinuclear NMR, ESI-TOF-MS/ESI-FTMS, and elemental analysis. MMFF force-field simulations indicates that all metallodendrimers have a hexagonal ring with an internal radius of approximately 1.4 nm.