The homoleptic silver(I) compound [PPh₄][CF₃AgCF₃] (1) provides a convenient entry to the homoleptic silver(III) derivative [PPh₄][Ag(CF₃)₄] (2). Once isolated as pure substances, these compounds exhibit marked thermal stabilities. Their structural and spectroscopic properties have been experimentally established. Moreover, their electronic structures have been calculated by theoretical methods. The electronic structure of the oxidized species [Ag(CF₃)₄]^- provides a new case of ligand-field inversion caused by the CF₃ ligands.