The coordination properties of the 2-[(diphenylphosphanyl)methyl]pyridine N,P-dioxide ligand towards three different silver(I) salts are described. The molecular structures of the coordination complexes obtained showed a strong dependence on the 2-[(diphenylphosphanyl)methyl]pyridine N,P-dioxide ligand and the binding ability of the counterion. The strongly binding trifluoroacetate ion yielded a unique planar silver cluster complex, whereas the less strongly binding triflate and BF4– complexes yielded polymeric structures. The synthesized complexes were fully characterized by elemental analysis and multinuclear NMR spectroscopy techniques. The crystal structures were determined by single-crystal X-ray crystallography.