We disclose a silver-catalyzed trifluoromethoxylation of N-tosyl aziridines with trifluoromethyl arylsulfonate. The protocol is characterized by its mild conditions, simple operations, and good chemo- and regioselectivity. In addition, the trifluoromethoxylation of trisubstituted aziridines could construct C-OCF3 quaternary centers exclusively, which is quite rare. This method unlocks a new catalytic blueprint for accessing β-trifluoromethoxylated amines, which could be important building blocks in synthetic chemistry.