The copper‐catalyzed radical aminofluorination of styrenes with N‐fluorobenzenesulfonimide (NFSI) is realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite that of the palladium‐catalyzed and noncatalyzed processes. Preliminary mechanistic studies suggested the reaction went through a radical pathway and was supported by DFT calculations. In these reactions, NFSI is utilized as both a radical nitrogen source and radical fluorine source, thus rendering it an attractive reagent. Double agent: The copper‐catalyzed radical aminofluorination of styrenes with N‐fluorobenzenesulfonimide (NFSI) has been realized with high regioselectivity, thus affording aminofluorination products with regioselectivities opposite to those of the palladium‐catalyzed and noncatalyzed processes. NFSI reacts under NF bond homolysis and is utilized as both a radical nitrogen source and radical fluorine source.