Ultramicroelectrode (UME) has a rapid response time to obtain electrochemical transient information. To obtain the real-time transient Raman information, we introduce the Au UMEs into the measurements of electrochemical surface-enhanced Raman spectroscopy (EC-SERS). However, the SEM and electrochemical results show that the roughened Au UMEs by conventional procedure for macroelectrodes will produce a microcavity because the enhanced mass transfer makes Au dissolved irreversibly. Thus, a roughening program based on pulse potential voltammetry is proposed to improve SERS activity of Au UMEs. We find a porous nanostructured film can be formed on the surface of Au UMEs, which exhibits good stability and stronger intensity in the EC-SERS experiments.