The involvement of silver in two-electron processes Ag(I/III) is currently emerging. However, the range of stability of the required and uncommon Ag(III) species is virtually unknown. Here, the stability of Ag(III) towards the whole set of halide ligands in the organosilver(III) complex frame [(CF₃)₃AgX]^- is theoretically analyzed (X = F to At). Even the softest and least electronegative halides (I and At) are found to form reasonably stable Ag(III)–X bonds. Our estimates were confirmed by experiment. In fact, the whole series of non-radiative halide complexes [PPh₄][(CF₃)₃AgX] (X = F to I) has been experimentally prepared and isolated in pure form. The pseudohalides [PPh₄][(CF₃)₃AgCN] and [PPh₄][(CF₃)₃AgN₃] have also been isolated, the latter being the first silver(III) azido-complex. Except for the iodo-compound, the crystal structures have been established by X-ray diffraction methods. The decomposition paths of the [(CF₃)₃AgX]^- entities at the unimolecular level have been examined in the gas phase by multistage mass spectrometry (MSn). The experimental detection of the two series of mixed complexes [CF₃AgX]^- and [FAgX]^- arising from the corresponding parent species [(CF₃)₃AgX]^- demonstrates that the Ag–X bond is particularly robust. Our experimental observations are rationalized with the aid of theoretical methods. Smooth variation with the electronegativity of X is also observed in the thermolyses of bulk samples. The experimentally established compatibility of Ag(III) with the heaviest halides is of particular relevance to silver-mediated or -catalyzed processes.