This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO<sub>2sub>F<sub>2sub>) and tetramethylammonium fluoride (NMe<sub>4sub>F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe<sub>4sub>F proceeds under mild conditions (often at room temperature) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO<sub>2sub>F<sub>2sub> and NMe<sub>4sub>F. Ab initio calculations suggest that carbon–fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.