The electrochemistry of three surfactants has been studied by voltammetry at boron doped diamond (BDD) electrode in sodium sulphate solutions. The electrochemical behaviour of these surfactants is characterized by an oxidation signal (peak or wave) situated before the electrolyte oxidation. The anodic current is found to follow a linear relation with the concentration of the surfactants; the slope decreases abruptly above the critical micellar concentration (CMC) of the surfactants. The CMC values obtained for an anionic (sodium dodecylbenzenesulfonate, SDBS), a cationic (polyoxyethylene-23-dodecyl ether, BRIJ 35) and a neutral (1-(hexadecyl)trimethylammonium bromide, CTAB) surfactant are found in good agreement with those measured by the classical technique of surface tension. This voltammetric method has the advantage not to require the use of a redox active electrochemical probe.