Voltammetric characterisations of cobalt, iron, manganese, nickel and zinc phthalocyanine complexes tetra substituted with benzyl- and dodecyl-mercapto ring substituents and immobilisation on gold electrodes via the self-assembling technique are presented. The self-assembled films are stable and showed blocking characteristics towards the following Faradaic processes; gold surface oxidation, under potential deposition of copper and solution redox chemistry of [Fe(H2O)63+]/[Fe(H2O)62+]. The solution chemistry of [Fe(CN) 6 ] −3 /[Fe(CN) 6 ] −4 redox process was used to study the orientation of the CoPcs-SAMs and this revealed a possible deviation from flat orientation of the complexes on the gold electrodes when the SAM formation times were greater than 24h. For SAM formation time at 24 and 48h, CoTDMPc-SAM showed more inhibition of the [Fe(CN) 6 ] −3 /[Fe(CN) 6 ] −4 redox process than the CoTBMPc-SAM counterpart, indicating more blocking characteristics of the dodecylmercapto ring substituents compared to the benzylmercapto counterpart. To avoid SAM desorption, the potential application should be limited to −0.2 to +0.8V vs. Ag∣AgCl (NaCl, sat’d) in acidic and neutral pH.