We report the first practical use of SF6 as a fluorinating reagent in organic synthesis. Photoredox catalysis enables the in situ conversion of SF6, an inert gas, into an active fluorinating species by using visible light. Under these conditions, deoxyfluorination of allylic alcohols is effected with high chemoselectivity and is tolerant of a wide range of functional groups. Application of the methodology in a continuous-flow setup achieves comparable yields to those obtained with a batch setup, while providing drastically increased material throughput of valuable allylic fluoride products.