Consecutive intramolecular desymmetrization and kinetic resolution of 2-substituted N-phenoxycarbonylserinols have been achieved in one-pot by a single chiral catalyst, bisox)-CuCl2, to form oxazolidinones with remarkable enantioselectivities (94-99% ee) as tert-alkylamine building blocks. The process culminates in a dual-function of the chiral catalyst.