This work describes the employment of discrete “AgCF3” complexes as efficient transmetalating agents to PdIIto surmount overlooked challenges related to the transmetalation step in Pd- catalyzed trifluoromethylation processes. We report the participation of a unique silver ate (Cs)[Ag(CF3)2] complex, under stoichiometric and catalytic conditions, in the unprecedented one-pot formation of PhCF3 using PhI as starting material. Moreover, we show that the transmetalation step, which is often ignored in these transformations, can also determine the success or failure of the coupling process.