The influence of mechanical stress on the electrochemical properties of ferritic steel SAE 1008 and austenitic stainless steel 301LN was studied using Scanning Kelvin Probe and Localized Electrochemical Impedance Spectroscopy (LEIS) techniques. The probe-working electrode Volta potential difference was mapped in situ under load. It was found that the influence of elastic deformation on the potential was small. Plastic deformation decreased the potential of steel by 150–300 mV, whereas the relaxation of the load from the plastic domain increased the Volta potential. However, some locations, which can contain residual stress, remained at low potential. The pre-strained surfaces were characterized by X-ray Photo Electronic Spectroscopy and by Atomic Force Microscopy. Distribution of the capacitance across strained and strain-free surfaces was studied by LEIS in boric/borate electrolyte. The plastic stress increases the capacitance and decreases the ability of the steels to passivate the surface indicating that emerging of pileups of dislocations create defective oxide films.