Microscopic studies on electrolyte solution / electrode interfaces provide the most fundamental information not only for understanding the electric double layer formed at the interfaces but also for designing sophisticated electrochemical (EC) devices. In this study, we developed tip-enhanced Raman spectroscopy (TERS), which is based on an electrochemical scanning tunneling microscope (EC-STM), and demonstrated electrochemical TERS (EC-TERS) measurements of benzenethiol monolayers on Au(111). A specially-designed cell enables us to carry out reproducible EC, EC-STM, and EC-TERS measurements, which indicates consistent results among these techniques for the oxidative desorption of the benzenethiol monolayers.