We have shown that the Cr deposition process at (La,Sr)MnO3 (LSM) and (La,Sr)(Co,Fe)O-3 (LSCF) cathodes of solid oxide fuel cells (SOFCs) is kinetically limited by the nucleation reaction between the gaseous Cr species and nucleation agents. In the case of the LSM electrode, the nucleation agent has been identified to be manganese species generated under cathodic polarization, and for the LSCF electrode, it is SrO species segregated at the electrode surface. Based on the mechanism proposed, we select La(Ni,Fe)O-3 (LNF) and (La,Ba)(Co,Fe)O-3 (LBCF) perovskites. The results show that LNF and LBCF electrodes are highly tolerant toward the Cr deposition and are much more stable than LSM and LSCF cathodes under SOFC operating conditions in the presence of a Fe-Cr metallic interconnect. (c) 2008 The Electrochemical Society.