Reactions between a N6O4 macrocyclic ligand (L1) and several Zn(II) salts (trifluoromethane sulfonate, p-toluenesulfonate, acetate, benzoate, o-, m- or p-hydroxybenzoate) led to the formation of seven complexes, [Zn2L1 (DMSO)4](OSO2CF3)4 (1), [Zn2(p-OSO2PhCH3)4L1] (2), [Zn2(OCOCH3)4L1] (3), [Zn2(OCOPh)4L1] (4), [Zn2(o-OCOPhOH)4L1] (5), [Zn2(m-OCOPhOH)4 L1] (6) and [Zn2(p-OCOPhOH)4 L1] (7), which were characterized by elemental analysis, 1H-NMR, 13C-NMR, IR, fluorescence spectroscopies and single crystal X-ray diffraction. In 1, the Zn atom is pentacoordinated with a N3O2 irregular trigonal bipyramidal coordination environment, like the geometries in compounds 3–7, whereas in structure 2 the metal atom is envisaged as possessing a distorted N3O3 octahedronal environment. All the compounds show interesting photoluminescent properties in solid states and solutions in DMF and DMSO, which are reported along with their TG-DTA thermal decomposition processes, UV-vis absorption spectroscopy and fluorescence quantum yields in DMF and DMSO.