Reaction of AgNO3 and 2,2′-bipyridine (bipy) under ultrasonic treatment gave the title compound, [Ag(C10H8N2)(NH3)]NO3. The crystal structure consists of dimers formed by two symmetry-related AgI–bipy monomers connected through intra-dimer π–π stacking and ligand-unsupported Ag⋯Ag interactions. A crystallographic C2 axis passes through the mid-point of and is perpendicular to the Ag⋯Agi(−x + 1, y, −z + ) axis. In addition, each AgI cation is coordinated by one chelating bipy ligand and one ammine ligand, giving a trigonal coordination environment capped by the symmetry-equivalent Ag atom. Molecules are assembled by Ag⋯Ag, π–π, hydrogen-bond (N—H⋯O and C—H⋯O) and weak Ag⋯π interactions into a three-dimensional framework. Comparing the products synthesized under different mechanical treatments, we found that reaction conditions have a significant influence on the resulting structures. The luminescence properties of the title compound are also discussed.