Anion-controlled endo- and exocyclic complexes were afforded in the reactions of an S2O3 macrocycle with AgPF6 and AgClO4, respectively. The two coordination modes that provide the Ag ion position inside (by PF6-) or outside (by ClO4-) the macrocyclic cavity are explained by the anion-coordination ability toward the metal cation. Furthermore, each Ag center bridges two ligands via a regular coordinative bond or by pi coordination, forming a cyclic dimeric-type product. NMR titrations of the complex system in solution were also carried out.