Pentafluorosulfanylation is a powerful boost of molecular properties for many applications. In order to leverage its full potential, a direct and high-yielding synthetic strategy is in great demand. We report here how the discovery of a direct pentafluorosulfanylation of thiolated arenes led to a generalized synthetic approach toward aryl– and heteroaryl pentafluorosulfanyl (SF5) compounds from various common building blocks. The combination of onium halides with silver(II) fluoride (AgF2) provided drastically enhanced oxidative fluorination conditions that enabled the single-step conversion of various thiophenol derivatives to SF5-compounds in high yields and broad scope. The particularly high reaction rate is accounted to an onium fluoroargentate(II)-mediated fluorination mechanism. The recycling potential of inorganic silver byproducts furthermore offers an avenue into industrial-scale production.