(1) Cytochromes c3 from Desulfovibrio vulgaris (Hildenborough strain) and Desulfovibrio desulfuricans (Norway strain) have been studied by differential pulse polarography and spectroelectrochemical method. Both cytochromes exhibit two reduction potential values Eh approximately --0.25 and --0.34 V (D. vulgaris), Eh approximately --0.16 and --0.34 V (D. desulfuricans). (2) Titrations by dithionite and controlled potential electrolysis coupled with polarography and spectrophotometry suggest that in both cases electronic exchanges are rapid.