In the present study, the stability constants of silver(I) coordination compounds with 2,2′-bipyridyl (bpy, L) in mixed methanol–acetonitrile solvents (MeOH-AN, χAN = 0.0 ÷ 1.0 mol fr.) were determined by the potentiometric method at 25.0 °C. The influence of reagents solvation on the change in stability of [Ag(bpy)]+ and [Ag(bpy)2]+ complexes upon changing the composition of the solvent MeOH→(MeOH-AN) was analyzed. It has been established that the determining factor in the shift of the complex formation equilibrium along the first and second steps of coordination with a change in the composition of the solvent is the contribution from the central ion resolvation. The obtained results and data on the thermodynamics of complex formation reactions of Ag+ with bpy and pyridine (py, L) in a few binary non-aqueous solvents were compared. The possibility of carrying out an estimated calculation of the stability constants of [Ag(L)]+ in non-aqueous solvents was confirmed.