Dehydrogenative coupling of arenes with fluoroaryl nucleophiles enables the efficient synthesis of fluoroaromatic compounds from readily available starting materials. Although considerable progress has been made in direct C(sp²)–H bond polyfluoroarylation, significant limitations in the regioselective functionalization of complex molecules and the scope of Ar^F groups still exist. We report here a highly selective method to address these long-standing limitations via a tandem activation/cross-coupling strategy. This method tolerates a wide range of arenes, pharmaceutically relevant aromatic compounds and polyfluoroaryl nucleophiles.