Di-μ-thiocyanato-bis[diamminesilver(I)], [Ag2(μ-SCN)2(NH3)4], was synthesized by the reaction of AgSCN with anhydrous liquid ammonia. In the binuclear molecule, the AgI atom is coordinated by two ammine ligands and the S atom of one thiocyanate ligand. Two of these [Ag(SCN)(NH3)2] units are bridged by the S atoms of the thiocyanate anions at longer distances, leading to a dimer with point group symmetry C2. The distance between the AgI atoms in the dimer is at 3.0927 (6) Å within the range of argentophilic interactions. The crystal structure displays N—H...N and N—H...S hydrogen-bonding interactions that build up a three-dimensional network.