Assembly of di[4-(pyridin-3-yl)pyrimidinyl]disulfide (3-ppds) with different metal salts resulted in a variety of coordination polymers that were structurally elucidated. For MnCl2, a 1-D repeated rhomboidal chain structure [MnCl2(3-ppds)2] n (1) was obtained, whereas a 1-D helical chain structure [Zn(NO3)2(3-ppds)] n (2) was built from Zn(NO3)2. A 1-D zigzag chain structure [Cu2(OAc)4(3-ppds)] n (3) was produced from Cu(OAc)2. In all three complexes, the 3-ppds ligand plays the same role as a bis(monodentate) bridging linker but with variations in both C–S–S–C torsion angles and dihedral angles defined by its conjugated heteroaromatic rings (pyrimidine and pyridine). The luminescence properties of the complexes have been evaluated in the solid state.