Abstract: Since ourfirst report on a metal-cornered molecular square (JACS, 1990, 112, 5645), we have been working on molecular self-assembly based on coordination chemistry. We have shown the highly efficient self-assembly of various cages and capsules with large cavities. In this talk, the self-assembly of giant, MnL2n coordination polyhedra from palladium ions (M) and curved bridging ligands (L) will be discussed, focusing on the mechanism, structures and functions of multicomponent self-assembled systems. Their structures are highly sensitive to the ligand structures and we observed a critical switch between M24L48 and M12L24 structures by a subtle change in the ligand bend angle. We note that the amplification of a small initial difference into an incommensurable difference in the resultant structures is a key mark of emergent behavior. Functionalization at the periphery and the interior of the giant spheres will be also discussed. Major references include: Science 2006, 313, 1273; Nature Chem. 2010, 2, 25; Science 2010, 328, 1144; Nature Chem. 2012, 4, 330.