An efficient and straightforward approach towards the synthesis of 1-alkyl-2-(trifluoromethyl)aziridines starting from 1,1,1-trifluoroacetoneviaimination, α-chlorination, hydride reduction and ring closure was developed. In addition, novel primary β-iodo amines were obtained by regioselective ring opening of these 2-(trifluoromethyl)aziridines using alkyl iodides, and their synthetic potential was demonstrated by converting them into novel α-CF₃-β-phenylethylamines upon treatment with lithium diphenylcuprate.