The enantioselective intramolecular oxyamination of unsaturated alkoxyamines using a hybrid catalytic system consisting of Cp*RhIII/chiral disulfonate/CuOAc is described. Tetrahydrofuran derivatives with a tetrasubstituted chiral center were obtained under the optimized conditions in 91:9–97:3 er. The use of a sterically hindered chiral disulfonate and a Cu additive was essential for the high enantioselectivity.