This communication describes a highly conducting, single-component molecular material [Ag₂(ophen)₂] (Hophen = 1H-[1,10]phenanthrolin-2-one) based on very strong off-set π-π stacking interactions with an unusually short ring-to-ring distance of ca. 3.15 Å between adjacent molecules and silver(I)-π interactions with the Ag⋯C contact of 3.082 Å between adjacent molecules. The title compound, having a room-temperature conductivity of 14 S cm^-1, is structurally different from both the known conducting single-component molecular materials of transition-metal complexes with sulfur-containing π-delocalized dithiolene ligands and the known conducting multicomponent organosilver(I) materials.