An N₂O₂S₂-macrocycle (L)^1,2 incorporating one pyridine and two benzo subunit was employed and their silver(I) and copper(I) complexes are reported. Reaction of L with AgPF₆ afforded a typical endocyclic complex [Ag(L)(PF₆)] (1). In the mole-ratio variation experiments, the use of six equivalents or above amount of AgPF₆ gave an endo/exocyclic 1D coordination polymer {[Ag₄(L)₂](PF₆)₄∙2CH₂Cl₂}_n (2a), in which the endocyclic complex units are linked by the exocyclic silver(I) ions to form an (L-Ag)-Ag-(L-Ag)-Ag pattern. In addition, when single crystals of 2a was undisturbed in air, the lattice solvent molecules were removed to form {[Ag₄(L)₂(PF₆)₂](PF₆)₂}_n (2b) accompanying the change of the coordination environments involving the anions in a single-crystal to single-crystal (SCSC) manner. Meanwhile, reactions of L with CuI in the presence of CF₃COOH gave an emissive coordination polymer {[Cu₄I₄(L)₂]∙2CF₃COOH}_n (3) with a double-stranded 1D chain structure linked by cubane-type Cu₄I₄ clusters.