We report on gold-catalyzed oxygen transfer utilizing, for the first time, electron-deficient trifluoromethylated alkynes as substrates. This double O-transfer process provides a direct and convenient one-step route to difficult-to-obtain trifluoromethylated 1,2-diketones. Due to the relatively mild oxidative reaction conditions (rt to 60 °C, 2,6-dichloropyridine N-oxide as an oxidizer, 3 mol % JohnPhosAuNTf2), various functional substituents were tolerated (19 examples; yields up to 95%). The synthetic utility of the obtained trifluoromethylated dicarbonyl products was further explored, and these studies included one-pot multicomponent syntheses of valuable CF3-substituted indoles and benzofurans.