It is shown that an electrochemically-driven oxide overcoating substantially improves the performance of metal electrodes in high-temperature electrochemical applications. As a case study, Pt thin films are overcoated with (Pr,Ce)O2-delta (PCO) by means of a cathodic electrochemical deposition process that produces nanostructured oxide layers with a high specific surface area and uniform metal coverage and then the coated films are examined as an O-2-electrode for thin-film-based solid oxide fuel cells. The combination of excellent conductivity, reactivity, and durability of PCO dramatically improves the oxygen reduction reaction rate while maintaining the nanoscale architecture of PCO layers and thus the performance of the PCO-coated Pt thin-film electrodes at high temperatures. As a result, with an oxide coating step lasting only 5 min, the electrode resistance is successfully reduced by more than 1000 times at 500 degrees C in air. These observations provide a new direction for the design of high-performance electrodes for high-temperature electrochemical cells.