Various β‐arylethylamine derivatives were straightforwardly obtained by the lithium‐catalyzed anti‐Markovnikov selective intermolecular hydroamination reaction of secondary aliphatic amines with vinylarenes. The use of only 1.5 mol % LiCH2TMS as a solid base in THF proved to be efficient to deliver the target products at room temperature with up to complete conversions. Both reaction partners were, moreover, used in equivalent amounts; thus, this protocol best respects the concepts of sustainable chemistry for the easy preparation of lead structures for pharmaceutically active compounds.