Perfluoroalkylated α-amino acids (PFAAs) are a unique class of compounds for biochemistry and pharmaceutical science. In this context, we report the successful intermolecular coupling of the Belokon’s chiral dehydroalanine Ni(II) complex with a variety of perfluoroalkyl iodides. A 4-cyanopyridine/B2Pin2 catalytic system generates perfluoroalkyl radicals, which after trapping by the ligand sphere of a chiral Ni(II) complex provide the diastereomeric complexes with up to >20 : 1 dr (seven examples). The obtained major (S,S)-diastereomers were easily isolated by simple silica column chromatography in 33–54 % yields. The perfluoroalkylated α-AA was subsequently released from the obtained Ni(II) complex through aqueous HCl treatment. The chiral auxiliary ligand ((S)-BPB=(S)-2-(N-benzylprolyl)aminobenzophenone) can be easily recycled after the acidic complex decomposition and reused for the synthesis of the starting dehydroalanine Ni(II) complex. © 2020 Wiley-VHCA AG, Zurich, Switzerland