Herein we report the mechanism of oxidative addition of CF3I to Au(I), and remarkably fast C-aryl-CF3 bond reductive elimination from Au(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR' (R = Cy, R' = 3,5-F-2-C6H4, 4-F-C6H4, C6H5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R' = 4-F-C6H4, 4-Me-C6H4). When R' = aryl, complexes of the type R3PAu(aryl)(CF3)I can be isolated and characterized. Mechanistic studies suggest that near-ultraviolet light (lambda(max) = 313 nm) photoinitiates a radical chain reaction by exciting CF3I. Complexes supported by PPh3 undergo reversible phosphine dissociation at 110 degrees C to generate a three-coordinate intermediate that undergoes slow reductive elimination. These processes are quantitative and heavily favor C-aryl-I reductive elimination over C-aryl-CF3 reductive elimination. Silver-mediated halide abstraction from all complexes of the type R3PAu(ary1)(CF3)I results in quantitative formation of Ar-CF3 in less than 1 min at temperatures as low as -10 degrees C.