The present work demonstrates the possibility to achieve asymmetric stereodivergency by means of a switchable asymmetric copper catalyst engaged in two transformations. The four stereoisomers of an amino alcohol are accessible one-pot, representing a totally new approach which notably avoids the purification process required when two enantiomers of a nonswitchable catalyst are needed for each step of a sequential catalytic process. The approach is made possible by the incorporation of an achiral benzene-1,3,5-tricarboxamide (BTA) phosphine ligand in a supramolecular terpolymer for which the optical purity and handedness are controlled by an enantiopure BTA monomer derived from Leucine. The work benefits from the fact that the direction of the asymmetric reaction is directly ) or the BTA helical catalyst with opposite handednesses for the HS and HA reactions (left, entries 5-6 of Table ).