The electrochemical decomposition of free and vanadyl tetraphenyl porphyrin in xylene solutions, and in the presence of water, using K2SO4 as electrolyte, was studied. Electrolysis of the two-phase system was carried out at constant current density and potential. It was observed that the electrochemical decomposition of the porphyrins, using a two-phase liquid system, is possible. An inexpensive organic solvent (xylene instead of THF, acetonitrile, methylene chloride etc.) can be very effectively used in such a system. The decomposition occurs through an oxidation process, with the subsequent formation of cationic and dicationic radicals, and a final breakdown of the macrocycle.