Highly sensitive surface-enhanced Raman spectroscopy (SERS) with additional functionality has recently attracted growing interest; however, it has been demonstrated experimentally in only a few microscopic systems. Here, we develop a novel SERS platform with three-dimensional nanostructure gold electrodes using competitive self-assembly between dielectrophoresis and convective aggregation. Appropriate conditions are able to provide the gold electrode with a higher order nanostructure to achieve in situ highly sensitive SERS of analytes. As such, our approach could enable the development of active functional control devices for in situ SERS.