A combined system of Raman spectroscopy and STM has been set up, which enables the two techniques to in-situ study electrochemical interfaces simultaneously, An optical fiber head carrying one excitation fiber and five collection fibers can be adjusted to approach to an advanced originally designed STM unit so that the STM tip above the sample electrode are surrounded by the sir fibers. The strong thermal interface by the laser illumination was avoided with the short acquisition time for SERS measurements by using optical multichannel analyzer. In-situ SERS spectrum of SCN- adsorbed on Ag electrode surface has been simultaneously recorded during STM imaging. The STM imaging taken before, during and after the SERS measurements have drifted from each other within 5%, which shows that the combined system is of satisfied over all stability.
