Silver(I) complexes with four symmetrically substituted O,O′-dialkyl derivatives of dithiophosphoric acid of the general formula [Ag{S2P(OR)2}] n (R = C2H5, i-C3H7, C4H9, and s-C4H9) were obtained. Their structures and spectroscopic characteristics were studied by solid-state 13C and 31P CP/MAS NMR spectroscopy and X-ray diffraction analysis. The parameters of the anisotropy of the 31P chemical shift 31P-δ aniso and η (δ aniso is the chemical shift anisotropy and η is the asymmetry parameter) calculated from the diagrams of the x 2-statistic revealed that the (RO)2PS2 groups act as bridging ligands in all the silver(I) complexes obtained. The hexanuclear complex [Ag6{S2P(O-i-C3H7)2}6] was found to form two modifications α and β. According to the X-ray diffraction data, the silver(I) complex with O,O′-di-s-butyl dithiophosphate exists as discrete hexanuclear molecules [Ag6{S2P(O-s-C4H9)2}6]. In the clear molecules β-[Ag6{S2P(O-i-C3H7)2}6], the signals for the phosphorus atoms were assigned to their positions determined from the X-ray diffraction data.