Significance Compounds bearing trifluoromethyl groups are of interest in areas such as material chemistry and pharmaceuticals. Despite such widespread use of trifluoromethyl moieties, relatively few reliable methods of trifluoromethylation exist. Furthermore, trifluoromethylation of terminal alkynes have been a difficult task. The authors report an oxidative trifluoromethylation ( 1 → 2 ) with large substrate scope, which allows for a facile trifluoromethylation of terminal alkynes.