We report herein a novel photoredox-catalyzed synthesis of allylic trifluoromethanes. The use of sulfilimino iminium as source of trifluoromethyl radical proves crucial to achieve high selectivity. Importantly, both styrene derivatives and unactivated alkenes are for the first time suitable partners for this process. The mild reaction conditions are compatible with a variety of functional groups. Remarkably, this method is readily broadened to other perfluoroalkyl groups (RF = CFCl2, CF2Br, C4F9). An extensive mechanistic study is also provided.