Slow diffusion of AgX with O(SiMe2(4-Py))2 (L) yields unique molecular rectangles consisting of [Ag(L)]2X2 (X- = NO3-, ClO4-, PF6-, and CF3SO3-). For the rectangular system, the transannular argentophilic (Ag−Ag) interaction competes with the interaction between Ag(I) and its anions, while the π−π interactions are constantly preserved. The strength of the argentophilic interaction is in the following order: NO3- > ClO4- > PF6- > CF3SO3- and is reversibly stretched via the anion exchange from 3.20(1) to 3.81(1) Å without the destruction of the cyclic skeleton.