Self-assembly is one of the most important and useful techniques for the convenient construction of nanostructures such as particles, fibers, layers, [1] which show a variety of attractive functional molecules and materials for use as a catalyst, sensor, material transporter, and optical material.[2] In most cases, the size and morphology of the nanostructure depend on the components, but the prediction of the overall structure of the nanostructure remains a difficult challenge. The supramolecular nanostructure based on dynamic and directed interactions between the components, such as hydrogen bonding, p-stacking, and coordination bonding with metal ions [3] has been widely used for the formation of shape-defined aggregations, such as wire [3] and tube [4] structures. Such a strategy showed great success for materials composed of a d-block metal complex known as metal-organic frameworks (MOFs).[5] Conversely, the number of reports on an aggregation composed of the f-block metal complex has been recently increasing because the assembly of lanthanide ions shows unique functions such as magnetic [6,7] and luminescent applications. [7] We reported the synthesis of the "trisaloph" ligand, a macrocyclic multidentate ligand composed of three saloph moieties, and its lanthanide-zinc heterotetranuclear complex.[8] Saloph ligands form planar complexes with a variety of metals, [9] which have been developed for supramolecular systems, such as anion-templated assemblies, [10] self-assembled fibers, [11] and liquid crystals.[12] The trisaloph ligand was also utilized as a module for a one-dimensional multi-metal supramolecule.[13] Alkali metal ions caused a stacked tubular aggregation of the trisaloph ligands due to p-p stacking and coordination to the metal ion.[13] The trisaloph lanthanide complex is expected to form a self-assembled aggregation due to the strong interaction between the metal ion and the counter anion of the cationic lanthanide complex that can act as a spacer ligand bridging the lanthanide because the rigid O6 site of the trisaloph fixes the vacant coordination sites of the lanthanide ion in a one-dimensional direction, that is, tailored to a fibril morphology. Herein, the unique aggregation of the trisaloph Zn II 3 La III complex bearing PEGylated adamantane units is successfully formed in an aqueous solution by complexation with b-cyclodextrin (b-CD). Additionally, the morphology of the nanostructure is controlled by coordinated anions based on the structural change in the trisaloph complex.All trisaloph ligands and their complexes reported thus far are insoluble in aqueous media. However, we designed and synthesized a trisaloph ligand bearing adamantane units as an appropriate candidate for water-soluble trisaloph metal complexes by taking advantage of the association of the adamantane units with b-CD.[14] The trisaloph complexes 1 (Figure 1) would be quite versatile because they should be soluble in organic solvents in the absence of b-CD due to high hydrophobicity of the adamantane units. Both aqueou...