A large 40-membered N4O4S4 macrocyde (L-2) was obtained through a 2:2 cyclization of the corresponding dithiol and dichloride as a minor product during the preparation of a 20-membered N2O2S2 macrocycle (L-1, 1:1 cyclization product). Each macrocyde was successfully separated from the mixed products and identified. The larger macrocyde L-2 allowed the preparation of its dimercury(I) complex, adopting a one-dimensional (1D) stairway-like polymeric chain linked with the anion. A monomercury(II) complex of the smaller macrocyde L-1 was also prepared. Both complexes and the larger macrocyde L-2 were structurally characterized by the single crystal X-ray analysis.