A 20-memberd N₂O₂S₂-macrocycle (L)^1,2 was employed and its mole-ratio dependent silver(I) complexes with different coordination modes and topologies are reported.³ When one equivalent of AgPF₆ was reacted with L, a typical endocyclic 1:1 complex [Ag(L)]PF₆ (1, see below) was afforded. While, the use of three equivalents or above amount of AgPF₆ gave an endo/exocyclic 1-D coordination polymer {Ag₄(L)₂](PF₆)₄∙2CH₂Cl₂}_n (2a, see below), in which the endocyclic complex units are linked by the -^endoAg-S-^exoAg-S- bond to form an infinite chain. Upon removal of the dichloromethane molecules in the crystal lattice of 2a in the ambient condition, conversion of the coordination geometry of the exocyclic Ag atom from linear (2a) to trigonal plane (2b, {[Ag₄(L)₂(PF₆)₂](PF₆)₂}_n, see below) as well as sliding of the 1-D chains were observed in a single-crystal-to-single-crystal manner.