A rationally designed sulfur-rich macrocycle L incorporating one pyridine and one benzo subunit was synthesized and structurally characterized. From the assembly reactions of L with copper(II) nitrate and mercury(II) iodide, an endocyclic monocopper(II) complex and an exocyclic dimercury(II) complex were prepared, respectively. On the basis of these results, the construction of a Hg(II)/Cu(II) heteronuclear 1D network complex with an endo/exocyclic coordination mode was achieved by one-pot assembly reaction of L with mercury(II) iodide in the presence of copper(II) nitrate.