Anion-controlled endo- and exocyclic complexes were afforded in the reactions of an S(2)O(3) macrocycle with AgPF(6) and AgClO(4), respectively. The two coordination modes that provide the Ag ion position inside (by PF(6)(-)) or outside (by ClO(4)(-)) 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.