The near-surface electronic structure of the room-temperature ionic liquid (RT-IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([EMIM][Tf2N]) has been investigated with the combination of the electron spectroscopies metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS (HeI and HeII)), and monochromatized X-ray photoelectron spectroscopy (XPS). We find that the top of the valence band states originates from states of the cation (see also ref 1). The ultimately surface-sensitive technique MIES proves that the surface layer consists of both cations and anions. The temperature dependence of the spectra has been measured between about 160 and 610 K. Information on the glass transition and the possibility for low-temperature distillation of [EMIM][Tf2N] at reduced pressures is derived from the present results.