Surface-decoration of perovskites can strongly affect the oxygen reduction activity, and therefore is a new and promising approach to improve SOFC cathode materials. In this study, we demonstrate that a small amount of secondary phase on a (001) La 0.8Sr 0.2CoO 3-δ (LSC) surface can either significantly activate or passivate the electrode. LSC (001) microelectrodes prepared by pulsed laser deposition on a (001)-oriented yttria-stabilized zirconia (YSZ) substrate were decorated with La-, Co-, and Sr-(hydr)oxides/carbonates. "Sr"-decoration with nanoparticle coverage in the range from 50% to 80% of the LSC surface enhanced the surface exchange coefficient, k q, by an order of magnitude while "La"- decoration and "Co"-decoration led to no change and reduction in k q, respectively. Although the physical origin for the enhancement is not fully understood, results from atomic force microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy suggest that the observed k q enhancement for "Sr"-decorated surfaces can be attributed largely to catalytically active interface regions between surface Sr-enriched particles and the LSC surface. © 2011 The Royal Society of Chemistry.