The influence of temperature on the electrodeposition of copper on alkanethiolate-covered Au(lll) was studied by means of cyclic voltammetry and in situ scanning tunneling microscopy (STM) in the temperature range from 300 to 345 K. We show that thermally induced defects allow for copper electrodeposition to occur much faster than at 300 K. Only at elevated temperatures can smooth copper layers be grown on the thiolated electrodes, independent of the thiolate chain length. The layerwise growth is mediated by a surfactant-libe action of the thiolate.