Over the last decades, trifluoromethyl copper(I) complexes have played a key role as reactive species in the formation of C–CF3 bond-forming reactions. This Short Review covers not only select examples of relevant Cumediated or catalyzed nucleophilic trifluoromethylation reactions, one of the most active fields in organic synthesis, but also provides a comprehensive picture of the real behavior of these copper species, including ubiquitous cuprates, in the reaction media.