Both azido (N3) and trifluoromethyl (CF3) groups are key moieties of numerous valuable molecules that are extensively applied in drug discovery, chemical biology, and synthetic chemistry. However, the asymmetric construction of chiral quaternary stereocenters bearing both N3 and CF3 groups is still unexplored. Herein, we report a kind of bench-stable and easily adjustable benziodazolone-based azidating reagents. These reagents were used to achieve an enantioselective copper-catalyzed azidation of N-unprotected 3-trifluoromethylated oxindoles to provide diverse enantioenriched 3-N3-3-CF3 oxindoles.