In this work, we synthesized silver(I) complexes with monosubstituted derivatives of the decahydro-closo-decaborate and dodecahydro-closo-dodecaborate anions of the composition [Ag(PPh3)4][B10H9OC5H10] (1), [Ag(PPh3)4][B10H9O2C4H8] (2), [(Ph3P)2Ag[μ–B12H11Cl]Ag(Ph3P)2] (3), and [(Ph3P)2Ag[μ–B10H9COOMe]Ag(Ph3P)2] (4). These compounds were obtained by the interaction between the tetrabutylammonium salts of the corresponding anions [B10H9OC5H10]−, [B10H9O2C4H8]−, [B10H9Cl]2−, and [B10H9COOCH3]2− with tris(triphenylphosphine)silver (I) nitrate in the presence of triphenylphosphine. The complexes synthesized were investigated using elemental analysis, IR, 1H and 13C NMR spectroscopies, and X-ray diffraction.