A series of three meso-tetra-alkyl porphyrins (H(2)TAPs) were synthesised and their electrochemical properties were studied in dichloromethane containing either tetra-butyl ammonium perclorate (TBAP) or tetra-butyl ammonium hexafluorophosphate TBA(PF6) as supporting electrolyte (SE) by cyclic voltammetry and in situ UV/vis spectroelectrochemistry. Values of E-1/2 for the recorded four redox processes of these porphyrins and of the meso-tetra-phenyl porphyrin (H2TPP) on glassy carbon and platinum were measured and compared. The redox data collected on the first oxidation and the first reduction processes predict that the value of Delta(LUMO - HOMO) for the H(2)TAPs is lower than for meso-tetra-phenyl porphyrin and, therefore, that the first Q band of the electronic spectra of the H(2)TAPs is red shifted relatively to the same band in the spectrum of H2TPP; this shift was indeed found. The second oxidation process of the H(2)TAPs is influenced by the supporting electrolyte used and the dication then formed is consumed by an irreversible chemical reaction. The species produced in this reaction is irreversibly reduced at a considerably lower potential. The electrochemical and spectroelectrochemical data collected are consistent with the occurrence of structural distortion in the macrocycle rings of the H(2)TAPs. (c) 2004 Elsevier Ltd. All rights reserved.