The electrochemical behavior of the natural (DPEP)VO series (where DPEP is the dianion deoxophylloerythroetioporphyrinate) is studied in methylene chloride. The investigated compounds, which were extracted from oil shales of Tarfaya (Morocco), exhibit a typical electrochemical behavior as compared to that of related synthetic vanadyl porphyrins. The electro-oxidation of (DPEP)VO is characterized by a splitting of the peaks when carried out at a glassy carbon electrode. This can be explained by two possible paths (CE and EC mechanisms) which are characterized by a “square diagram” where the chemical step, C, corresponds to a dimerization (radical–radical or substrate–substrate reaction). The electrochemical or chemical (AgBF4) oxidation gives a dimeric dicationic species [(DPEP)VO]22+ which was characterised by EPR and UV-visible spectroscopy. Modelling of the current–voltage curves was carried out and all thermodynamic and kinetics parameters relative to the proposed square diagram were determined.