The six-coordinated silver(I) complex [Au2Ag(mu-(PPh2)(2)py)(2)(OTf2 }(OTf), 4 (py = pyridine, OTf = CF3SO3), and the five-coordinated silver(I) complex [Au2Ag-(acetone)(mu-(PPh2)(2)py)(2)](PF6)(3), 6, were prepared by the reaction of the precursor complexes 1(OTf)(2) and 1(PF6)(2), in which 1 = [Au-2(mu-(PPh2)(2)py)(2)](2+), with 1 equiv of Ag(OTf) in dichloromethane and excess of Ag(PF6) in a mixture of dichloromethane/acetone, respectively. Also, the five-coordinated silver(I) complex {Au2Ag(p-(PPh2)(2)py)(2)(py)(OTf)]-(OTf)(2), 5, was obtained by the reaction of 4 with pyridine. The clusters 4-6 were characterized using multinuclear NMR spectroscopy and elemental microanalysis. The single-crystal X-ray diffraction analysis revealed the octahedral and distorted square pyramidal geometries around the silver(I) centers in the crystal structures of 4 and 6, respectively; a dynamic structure was observed for cluster 5 due to pendulum motion of the Ag(pyridine) moiety, which was anchored in the metallomacrocyclic unit [Au-2(mu-(PPh2)(2)py)(2)](2+). Although the crystal structure of 6 did not display disorders for the silver atom and the acetone ligand similar to that observed for 5, the low-temperature NMR spectroscopies and calculations show a dynamic structure for cluster 6 due to linear motion of the Ag(acetone) moiety. The reaction of the precursor complex 1(PO2F2)(2) with 2 equiv of Ag(PO2F2) yielded the tetranuclear Au2Ag2 cluster [Au2Ag2(PO2F2)(2) (mu-(PPh2)(2)py)(2)](PO2F2)(2), 7, with a planar-shaped {Au2Ag2} metal core in which alternating Au and Ag atoms occupy the tetragon vertices and showed a strong argentophillic interaction between the silver(I) centers. All clusters 4-7 are emissive in the solid state, and the origins of their emissive excited states were determined using time-dependent density functional theory calculations. Cluster 7 showed a dual phosphorescence emission, which displays strong dependence of the contributions of each emissive component onto the excitation wavelength.