Abstract A chemo‐selective copper(I)‐catalyzed oxytrifluoromethylation of N ‐Boc‐ynamides with TMSCF 3 has been achieved, affording the trifluoromethylated oxazolones in 51–99% yields. The reaction proceeds at room temperature and tolerates a variety of functional groups such as −X, −OMe, alkenyl, and other substituents. The resulting oxazolones provide access to α‐CF 3 ‐substituted amines through decarboxylative reduction. magnified image