CH‐π Multi‐Interaction‐Driven Recognition and Isolation of Planar Compounds in a Spheroidal Polyaromatic Cavity

π‐π Interactions are established as a powerful supramolecular tool, whereas the usability of CH‐π interactions has been rather limited so far. Here we present (i) selective binding of planar polyaromatics and (ii) effective isolation of planar metal complexes by a polyaromatic capsule, utilizing multiple CH‐π interactions. In the spheroidal cavity, one molecule of large and medium‐sized polyaromatic molecules (i. e., coronene and pyrene) is exclusively bound from mixtures bearing the same number of aromatic CH groups. Theoretical studies reveal that multiple host‐guest CH‐π interactions (up to 32 interactions) are the predominant driving force for the observed selectivity. In addition, one molecule of planar metal complexes (i. e., porphine and bis(acetylacetonato) Cu(II) complexes) is quantitatively bound by the capsule through aromatic and aliphatic CH‐π multi‐interactions, respectively. The ESR and theoretical studies demonstrate the isolation capability of the capsular framework and an unusual polar environment in the polyaromatic cavity.