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.