A method to produce a substrate suitable for surface-enhanced Raman study on the pure massive Rh electrodewas developed. The surface-enhanced Raman scattering (SERS) active Rh electrode with good stability,reversibility, and ease of preparation can be obtained by the control-current electrochemical roughening method.The surface enhancement factor was estimated to be 3 orders of magnitude. Such kind of enhancement allowsthe investigation of not only some molecules of large Raman cross-section (e.g., pyridine) but also othermolecules of very small Raman cross-section (like CO). This result shows that the Rh surface can be used asa useful substrate for the combined electrochemical and Raman study of some systems that are both offundamental and application interest.