Improvement of solid oxide fuel cells strongly relies on the development of cathode materials with high catalytic activity for the oxygen reduction reaction. Excellent activity was found for perovskite-type oxides such as La1−xSrxCoO3−δ (LSC), but performance degradation, probably caused by surface composition changes, hinders exploitation of the full potential of LSC. This study reveals that the potentially very high activity of the LSC surface can be traced back to few very active sites. Already tiny amounts of SrO, for example, 4% of a monolayer, deposited on an LSC surface, lead to severe deactivation. Co, on the other hand, causes (re-)activation, suggesting that active sites are strongly related to Co being present at the surface. These insights could be gained by a novel method to measure changes of the electrochemical performance of thin film electrodes in situ, while modifying their surface: impedance spectroscopy measurements during deposition of well-defined fractions of monolayers of Sr-, Co- and La-oxides by single laser pulses in a pulsed laser deposition chamber.