Here we report a new supramolecular strategy for the selective separation of specific polycyclic aromatic hydrocarbons (PAHs) from mixtures. The use of a triethylene glycol-functionalized formylpyridine subcomponent allowed the construction of an FeII4L4 tetrahedron 1 that was capable of transferring between water and nitromethane layers, driven by anion metathesis. Cage 1 selectively encapsulated coronene from among a mixture of eight different types of PAHs in nitromethane, bringing it into a new nitromethane phase by transiting through an intermediate water phase. The bound coronene was released from 1 upon addition of benzene, and both the cage and the purified coronene could be separated via further phase separation.