Water-soluble metalloporphyrazines (2, 3, and 4) bearing peripherally functionalized bis[thioethoxy(ethoxy)ethanol] moieties have been prepared from the corresponding [2H]-2,3,7,8,12,13,17,18-octakis{2-[2-2-hydroxyethoxy)ethoxy]-ethylthio}porphyrazine and appropriate metal salts [Zn(acac) 2 , CoCl 2 , MnCl 2 ] in non-aqueous polar solvents such as, alcohol and THF. Multifunctional polyetherolsulfanyl peripheral sites, the exocyclic site of porphyrazines, serve as weak interacting ionophore in a number of metal ions, such as Ag I and Pd II . The reactivity of the peripheral groups of MPzs was tested by spectrophotometric titration by Ag I and Pd II . The titration resulted in the formation of intractable less soluble black and dark-blue polynuclear porphyrazine complexes. The new compounds have been characterized by elemental analysis, FTIR, 1 H NMR, UV–vis and MS (MALDI-TOF). The voltammetric investigation of the complexes showed common ligand and metal-based redox processes.