Geometrically well-defined model electrodes have been employed to unambiguously elucidate the individual resistive and capacitive processes of various solid oxide fuel cell cathodes by means of impedance spectroscopy. The measurements were performed on dense, thin film-type microelectrodes of Equation or symbol description not availableLa1xSrxCo1yFeyO3δ and related perovskite-type materials prepared by pulsed laser deposition and photolithography. It was found that the substitution of the A-site cation La in Equation or symbol description not availableLa1xSrxCo1yFeyO3δ by Sm and especially by Ba leads to a strong enhancement of the surface exchange kinetics, whereas a variation of the Equation or symbol description not availableCoFe ratio between 0 and 1 has only little effect on this quantity at temperatures around Equation or symbol description not available750°C. Furthermore, it has been studied how the electrochemical activation effect, i.e., the strong reduction of the surface exchange resistance after application of a large dc bias, depends on composition.