A new iron-catalyzed three-component perfluoroalkylarylation of styrenes with alkyl halides and arenes has been established. Alkyl halides undergo halogen atom transfer with methyl radicals to form alkyl radicals in reactions initiated by a combination of tert-butyl peroxybenzoate and an iron catalyst, thus adducting to the olefins, which results in alkylarylation products. The protocol is compatible with a wide range of perfluoroalkyl and non-perfluoroalkyl halides, features excellent functional group tolerance, and enables the synthesis of structurally diverse 1,1-diaryl fluoro-substituted alkanes.