From the interaction between azole-type ligands L and AgX (X=NO 3 or ClO 4 ) or [AgX(PPh 3 ) n ] (X=Cl, n=3; X=MeSO 3 , n=2), new ionic mononuclear [Ag(L) 2 ]X and [Ag(PPh 3 ) 3 L][X] or neutral mono-([Ag(PPh 3 ) n L(X)]) or di-nuclear ([{Ag(PPh 3 )(L)(μ-X)} 2 ]) complexes have been obtained which have been characterized through elemental analysis, conductivity measurements, IR, 1 H NMR and, in some cases, also by 31 P{ 1 H} NMR spectroscopy, and single-crystal X-ray studies. Stoichiometries and molecular structures are dependent on the nature of the azole (steric hindrance and basicity), of the counter ion, and on the number of the P-donor ligands in the starting reactants. Solution data are consistent with partial dissociation of the complexes, occurring through breaking of both Ag–N and Ag–P bonds.