Interfacial oxidation of Nb and Si at 650 degrees C on Laves phase forming Ti-Nb stabilized ferritic stainless steel (Fe-19Cr-0.9Si-0.2Nb-0.1Ti (at.%), grade EN 1.4509) was studied by electrochemical impedance spectroscopy and photoelectron spectroscopy. It was found that excess Nb efficiently hinders the formation of electrically resistive SiO2 layer at the oxide-metal interface. The beneficial role of Nb was attributed to its high segregation rate and the formation of conductive oxides at the interface. However, the oxidation was strongly influenced by age-precipitation of the Laves (FeNbSi)-type intermetallic phase, which removed free Nb from the alloy solution and thus allowed SiO2 layer to form more easily. These results can be applied to optimize the oxide scale composition by Nb alloying of the ferritic stainless steel to maintain high performance under various operation conditions, particularly in solid oxide fuel cell applications. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.