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Abstract The interaction of perfluorinated molecules, also known as “forever chemicals” due to their pervasiveness, with their environment remains an important yet poorly understood topic. In this work, the self‐assembly of perfluorinated molecules with multivalent hosts, pillar‐[5]‐arenes, is investigated. It is found that perfluoroalkyl diacids and pillar‐[5]‐arenes rapidly and strongly complex with each other at aqueous interfaces, forming solid interfacially templated films. Their complexation is shown to be driven primarily by fluorophilic aggregation and assisted by electrostatic interactions, as supported by the crystal structure of the complexes, and leads to the formation of quasi‐2D phase‐separated films. This self‐assembly process can be further manipulated using aqueous two‐phase system microdroplets, enabling the controlled formation of 3D micro‐scaffolds.