A spectroscopic and structural investigation of binuclear silver(I) complexes supported by aliphatic phosphine ligands, namely [Ag(PCy3)(O2CCF3)](2) (1), [Ag-2(mu-dcpm)(2)]X-2 (X = CF3SO3, 2; PF6, 3; dcpm = bis(dicyclohexylphosphino)methane), and [Ag-2(mu-dcpm)(mu-O2CCF3)(2)] (4), is described. X-ray structural analyses of 1-4 reveal Ag-Ag separations of 3.095(1), 2.918 (av), 2.923 (av), and 2.8897(9) Angstrom, respectively. Due to the optical transparency of the phosphine ligands, the UV-vis absorption band at 261 nm in CH3CN for 2 and 3 is assigned to a 3 delta sigma* -> 5p sigma transition originating from Ag(I)-Ag(I) interactions. The argentophilic nature of this band is verified by the resonance Raman spectrum of 2 with 273.9 nm excitation, where virtually all of the Raman intensity appears in the Ag-Ag stretch fundamental (80 cm(-1)) and overtone bands. Complexes 2 and 3 exhibit photoluminescence in the solid state at room temperature.