A comparative study of the homoleptic [M(CF₃)₄]^- complexes of all three coinage metals (M = Cu, Ag, Au) reveals that homolytic M-C bond cleavage is favoured in every case upon excitation in the gas phase (CID-MS²). Homolysis also occurs in solution by photochemical excitation. Transfer of the photo-generated CF₃• radicals to both aryl and alkyl carbon atoms was also confirmed. The observed behaviour is rationalized attending to the electronic structure of the involved species, which all show ligand-field inversion. Moreover, the homolytic path gives experimental proof of the marked covalent character of the M-C bond. The relative stability of these M-C bonds has been evaluated by energy-resolved mass spectrometry (ERMS) and follows the order: Cu < Ag << Au. The qualitatively similar and rather uniform behaviour experimentally observed for all three coinage metals gives no ground to suggest variation in the metal oxidation state along the group.