We report herein a novel photoredox-catalyzed hydrotrifluoromethylation of unsaturated systems under continuous flow. This metal-free method is easily broadened to other perfluoroalkyl groups (RF = CF3, CFCl2, CF2Br, C4F9) thanks to the use of sulfilimino iminiums as sources of ·RF radicals. The mild reaction conditions are compatible with unactivated alkenes bearing a wide range of functionalities, as well as with alkynes for the first time.