β-[¹⁸F]fluoroamines were radiolabeled using anchimeric assistance of the amine. The ring opening of the aziridinium intermediate by different sources of nucleophilic fluoride at RT led to both fluorinated regioisomers with ¹⁸F-incorporation yields of up to 77% at RT. The radiofluorination 2-[¹⁸F]fluoroethylamines afforded single compounds from the alcohol precursor at RT.