Electrochemical measurements were performed to investigate the effectiveness of cationic surfactants of the N-alkyl quaternary ammonium salt type, i.e. myristyltrimethylammonium chloride (MTACl), cetyldimethylbenzylammonium chloride (CDBACl), and trioctylmethylammonium chloride (TOMACl), as corrosion inhibitors for type X4Cr13 ferritic stainless steel in 2 M H 2SO 4 solution. Potentiodynamic polarization measurements showed that these surfactants hinder both anodic and cathodic processes, i.e. act as mixed-type inhibitors. It was found that the adsorption of the N-alkyl ammonium ion in 2 M H 2SO 4 solution follows the Langmuir adsorption isotherm. Plots of log [ θ/(1 − θ)] versus log c inh yielded straight lines with a slope, which changed drastically at the critical micelle concentration (CMC) of the surfactants studied. Accordingly, the CMC could be accurately determined from these measurements. The calculated values of the free energy of adsorption Δ G ads are, in cases when the charge on the metal surface is negative with respect to the PZC, relatively high what is characteristically for the chemisorption. On the other hand, for positive metal surfaces it is assumed that SO 4 2− anions are adsorbed first, so the cationic species would be limited by the surface concentration of anions. Accordingly Δ G ads values were lower in this case and the adsorption is due to merely electrostatic attraction, which is characteristically of physisorption.