Corrosion processes occurring on stainless steel 304 surfaces under anodic polarization were characterized using scanning electrochemical microscopy (SECM) and the scanning vibrating electrode technique (SVET), complemented with conventional potentiodynamic polarization curves. Stable pit formation on the samples was monitored by SVET as result of surface modification under electrochemical control. The operation procedure may involve the previous electrochemical reduction of the passive oxide layer if the media is not aggressive enough to induce pitting at small overpotentials. Additionally, the sample generation - tip collection operation mode of the SECM enabled to detect local release of iron (II) ions, as well as their conversion to iron (III), both processes being greatly affected by the potential applied to the substrate. (C) 2014 Elsevier B.V. All rights reserved.