In this study, the performance improvement of the SOFC single cell and its underlying mechanism was investigated. Furthermore, an application of the identified electrochemical mechanism is proposed and tested experimentally. The deposition of Platinum (Pt) at electrochemically active sites for the oxygen reduction reaction is determined to be responsible for the improved performance. Pt migration from a current collector to the cathode active sites originates from the oxygen partial pressure difference between current collector and triple phase boundary, and the electrochemical reduction reaction. It is supported by the confirmation of Pt particles at the cathode active sites by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and calculations of the thermodynamic equilibrium partial pressure values. In addition, correlation of the initial performance change and the quantities of Pt deposition are investigated. This selective Pt deposition mechanism at the active sites is applied to the LSCF cathode, as well. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.