Tetrasubstituted metal-free {2H[Pc(S(CH 2 ) 6 OCOC 4 H 3 S) 4 ]} and copperphthalocyanine {Cu[Pc(S(CH 2 ) 6 OCOC 4 H 3 S) 4 ]}, bearing thiophene-2-carboxylate-hexylthio moieties, have been prepared as isomeric mixtures via cyclo-tetramerization. Both new compounds have been characterized by elemental analysis, FTIR, 1 H and 13 C NMR, MS (Maldi-TOF) and UV–Vis spectral data. The cation binding abilities of the functional phthalocyanines with Ag I , Pd II , Hg II , Pb II and Cd II are evaluated by a monomer–oligomer formation technique with UV–Vis spectroscopy. Spectroscopic properties of the complexes were affected strongly by the electron-donating sulfanyl units on the periphery. Cyclic voltammetry and differential pulse voltammetry studies show that both compounds give up to three ligand-based reduction processes and one ligand-based oxidation process having diffusion-controlled one-electron transfer properties.