Abstract: | We report tunable supramolecular self‐assemblies formed by water‐soluble pillar[n]arenes ( WPn s, n=5–7) and bipyridinium‐azobenzene guests. Nanoscale or microscale morphology of self‐assemblies in water was controlled by the host size of WPn . Supramolecular self‐assemblies could undergo morphology conversion under irradiation with UV light. |