Despite the known nucleophilic nature of [M(CF3)2]–(M = Cu, Ag, Au), their participation in trifluoromethylation reactions of aryl halides remains unexplored. Herein, we report, for the first time, the selective access to Cu(CF3)2 – species, ubiquitous in Cu-mediated trifluoromethylations, and we rationalize its complex mechanistic scenario and its behavior compared to its silver and gold congeners through a mixture of experimental and computational approaches.