Recently, ionic liquids (ILs) have attracted attention as prospective electrolytes for Li-ion batteries, with safe performance. Herein, the dynamics of the IL at the electrochemical interface, which is the key to the electrochemical reaction, was monitored using attenuated total reflectance far- and deep-ultraviolet (ATR-FUV-DUV) spectroscopy. An original measurement system, which combined an ATR-FUV-DUV spectrometer with a Kretschmann type (fully metal-coated prism) electrochemical setup, was assembled. Spectral measurements and assignments were performed for the 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([EMIM][TFSI])/Pt electrode (∼7 nm) interface. The incident light in the FUV and DUV regions entered a measurement system comprising an [EMIM][TFSI]/Pt electrode/ATR sapphire prism, and the potential-dependent absorption spectra were measured in the 180-450 nm range. This in-situ spectroscopic technique is unique in that the electronic transition spectra of the interfacial IL can be obtained. By switching the applied potentials, temporal spectral changes (i.e. relaxation signals) were tracked at wavelengths of 450 nm and 221 nm, where the direct electronic absorption of the IL was active and inactive, respectively. Comparing these relaxation times, it was revealed that the absorption signal at 221 nm changed more slowly than that at 450 nm. This indicated that the molecular conformations that affected the electronic absorption of the interfacial ILs changed slowly. Considering the surface-normal dipole selection rule for molecules on a metal surface, it is suggested that the slow changes in the molecular conformations can be ascribed to the potential-dependent interfacial orientations of [EMIM]+.