We report supramolecular repurposing of emtricitabine (FTC, trade name: Emtriva®), a blockbuster FDA-approved anti-HIV agent. FTC is revealed to act as a hydrogen-bonded cleft for bipyridine recognition. The supramolecular repurposing is realized by the generation of four cocrystals through liquid-assisted grinding. The clefts comprise discrete three-component assemblies sustained by a combination of hydrogen bonds and π⋯π interactions.