Electrode polarization and conductivity measurements were carried out at the Pd/YSZ interface and at conditions close to the Pd-PdO thermodynamic equilibrium. The steady-state current-overpotential characteristics were analyzed with a Butler-Volmer type of equation. Both, apparent exchange current density, I-o, and anodic/cathodic charge transfer coefficients (alpha(a)/alpha(c)), were calculated. Based on the experimental results, it was concluded that the charge transfer at the electrode is rate-determining in the case of PdO during anodic operation and Pd during cathodic operation, while in the other case mass transport of adsorbed oxygen species along the electrode/solid electrolyte interface is in competition with the charge transfer process. (c) 2006 Elsevier B.V. All rights reserved.