Fluorine in modern pharmaceuticals has enabled drugs with enhanced therapeutic value through the selective modulation of a variety of pharmacological parameters. Therefore, methods to prepare molecular scaffolds which contain the fluorine atom is of critical importance for the continued success of novel drug discovery. Toward this goal, the regioselective intermolecular aminofluorination of alkenes has been achieved with N,N-dialkylhydroxylamines and nucleophilic fluorine. With this copper-catalyzed approach, a variety of pharmaceutically relevant β-fluorophenethylamines have been prepared. Additionally, through the systematic evaluation of substituted alkenes and electronically varied O-substituted-N-hydroxylmorpholines, the limitations of the method have been discovered. Mechanistic experiments have also revealed the presence of a radical intermediate which suggests the transformation occurs through a nitrogen-initiated pathway.