In view of the assignment of the four redox potentials values to the four heme groups in the crystallographic structure of Desulfovibrio desulfuricans Norway cytochrome c3, a biochemical approach is reported. A singly modified cytochrome c3 on arginine 73 has been prepared. The study of the redox properties of the modified cytochrome by electrochemistry together with the graphic modelisation of the molecule allow to assign the highest redox potential (-165 mV) to the heme 4 in the three dimensional structure.