AzaPCs containing tetra- and octaguaiacol moieties have not been investigated up to now. In this study, an unusual method is used for the synthesis of metalloAzaPCs (M: Zn, Co, Cu) containing guaiacol moieties. All compounds are characterized by a combination of FT-IR, H-1 NMR, C-13 NMR, mass and UV/vis spectroscopy techniques. The molecular structure of starting pyrazine compounds 1 and 2 is also determined by the single crystal X-ray diffraction technique. The aggregation behavior of new Zn(II) AzaPCs is investigated in DMSO at different concentrations. The fluorescence properties of Zn(II) AzaPCs are investigated in different solvents. The fluorescence quantum yields of Zn(II) AzaPCs are calculated in DMSO.